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№27/2019
Norwegian Journal of development of the International Science
ISSN 3453-9875
VOL.1
It was established in November 2016 with support from the Norwegian Academy of Science.
DESCRIPTION
The Scientific journal “Norwegian Journal of development of the International Science” is issued 12 times a year
and is a scientific publication on topical problems of science.
Editor in chief – Karin Kristiansen (University of Oslo, Norway)
The assistant of theeditor in chief – Olof Hansen
 James Smith (University of Birmingham, UK)
 Kristian Nilsen (University Centre in Svalbard, Norway)
 Arne Jensen (Norwegian University of Science and Technology, Norway)
 Sander Svein (University of Tromsø, Norway)
 Lena Meyer (University of Gothenburg, Sweden)
 Hans Rasmussen (University of Southern Denmark, Denmark)
 Chantal Girard (ESC Rennes School of Business, France)
 Ann Claes (University of Groningen, Netherlands)
 Ingrid Karlsen (University of Oslo, Norway)
 Terje Gruterson (Norwegian Institute of Public Health, Norway)
 Sander Langfjord (University Hospital, Norway)
 Fredrik Mardosas (Oslo and Akershus University College, Norway)
 Emil Berger (Ministry of Agriculture and Food, Norway)
 Sofie Olsen (BioFokus, Norway)
 Rolf Ulrich Becker (University of Duisburg-Essen, Germany)
 Lutz Jäncke (University of Zürich, Switzerland)
 Elizabeth Davies (University of Glasgow, UK)
 Chan Jiang(Peking University, China)
and other independent experts
1000 copies
Norwegian Journal of development of the International Science
Iduns gate 4A, 0178, Oslo, Norway
email: publish@njd-iscience.com
site: http://www.njd-iscience.com
CONTENT
CHEMICAL SCIENCES
Asadov Z.,Zargarova S.,Zarbaliyeva I.
Rahimov R.,Huseynova S.
SYNTHESIS AND STUDY OF SURFACE-ACTIVE SALTS
BASED ON PROPOXY DERIVATIVES OF
HEXADECYLAMINE AND MONOCARBOXYLIC
ALIPHATIC ACIDS.........................................................3
Kholov Kh.,Samikhov Sh.
ACETYLTHIOUREA LEACHING GOLD FROM TAILS OF
FLOTATION DEPOSIT DZHIKIKRUT...............................7
Shibryaeva L.,Tertyshnaya Yu.,
Solovova Yu.Levina N.,Zhalnin E.
EFFECT OF PLANT ENVIRONMENT ON
DECOMPOSITION OF BIODEGRADABLE MATERIALS
BASED ON POLY-3-HYDROXYBUTYRATE AND
POLYLACTIDE.............................................................11
MEDICAL SCIENCES
Bodnya K.,Velieva T.,Bodnya I.
EVALUATION OF DEGREE OF IMMUNE DYSFUNCTION
AS OF CYTOKINES IN PATIENTS WITH LIVER
ECHINOCOCCOSIS .....................................................25
Gaponov K.
PECULIARITIES OF VITALITY IN ALCOHOL-ADDICTED
PATIENTS WITH DIFFERENT LEVELS OF PSYCHOSOCIAL
STRESS.......................................................................33
Pozdnyakova M.,Izmaylova T.
MALE INFERTILITY AS A MEDICAL AND SOCIAL
PROBLEM ..................................................................40
Nikolaeva I.,Radkevich L.
GENETIC AND ENVIRONMENTAL FACTORS FOR
THYROID CANCER......................................................42
Oprya Ye.
SYSTEM OF COMPLEX REHABILITATION OF PATIENTS
WITH SHYSOFRENIA IN VIEW OF SOMATIC
COMORBIDITY ...........................................................46
PHISICAL SCIENCES
Etkin V.
ENERGODYNAMIC THEORY OF GRAVITATION AND
LEVITATION ...............................................................51
Gladyshev G.
HIERARCHICAL TERMODYNAMICS RULES THE WORLD
TO THE EXTENT OF ITS APPLICABILITY ......................60
Norwegian Journal of development of the International Science No 27/2019 3
CHEMICAL SCIENCES
SYNTHESIS AND STUDY OF SURFACE-ACTIVE SALTS BASED ON PROPOXY DERIVATIVES OF
HEXADECYLAMINE AND MONOCARBOXYLIC ALIPHATIC ACIDS
Asadov Z.
Doctor of Chemical Sciences, professor, corresponding member
of Azerbaijan National Academy of Science; head of laboratory
of surfactants of Institute of Petrochemical Processes (IPCP)
Zargarova S.
Senior instructor of Baku Higher Oil School,
post-graduate researcher of laboratory of surfactants of IPCP
Zarbaliyeva I.
PhD (Chemistry), associate professor,
leading researcher of laboratory of surfactants of IPCP
Rahimov R.
Doctor of Chemical Sciences, associate professor,
chief researcher of laboratory of surfactants of IPCP
Huseynova S.
Scientific researcher of laboratory of surfactants of IPCP
Baku Azerbaijan
Abstract
Salts of the oligomeric propoxy derivatives of hexadecylamine with several organic acids were synthesized.
Structure and composition of the salts were confirmed by using IR spectroscopy. Surface tension and electrocon-
ductivity properties of the oligomers were examined and corresponding main parameters of the salts were calcu-
lated. Moreover, petrocollecting properties of these salts were determined and maximum values of petrocollecting
coefficients were calculated.
Keywords: hexadecylamine, propoxy derivative, salt, surfactant, petrocollecting
Introduction
The increasing demand to crude oil and products
of its refining results in ecological instability and dis-
balance. In order to improve ecological balance of the
nature, surfactants are used in industry including oil
production and refining [1,2]. Thin oil layers on the
surface of the water become one of such ecological
problems which may occur during transportation of
crude oil and its refining products.
According to the literature, higher aliphatic
amines may be used for synthesis of surface-active
compounds [3-5]. In a given study, surfactants are
obtained from hexadecylamine, propylene oxide and
monocarboxylic aliphatic acids. Main physical-chemi-
cal properties of the new surfactants including colloi-
dal-chemical ones were determined in order to apply
them as petrocollecting agents.
Experimental
Hexadecylamine was a product of “Alfa Aesar
GmbH & Co KG” firm (Germany) of purity > 98%.
Propylene oxide was a product “Organic Synthe-
sis” factory (Sumgayit, Azerbaijan) of 99.97-99.98%
purity.
Monocarboxylic aliphatic acids were “analytically
pure” grade products of Novocherkassk Plant of Syn-
thetic Products (Russia).
Potassium hydroxide was used as “analytically
pure” product of “Chemapol” firm (Czech Republic).
Oligomer of hexadecylamine and propylene oxide
was synthesized at 140-150o
C for 13-14 hours in an au-
toclave made of stainless steel and equipped with a reg-
ulator of temperature. In the given reaction, potassium
hydroxide was used as a catalyst. In the second step,
propoxy derivative of the hexadecylamine reacted with
different monocarboxylic aliphatic acids at 50-60o
C for
5-6 hours in order to obtain organic salts.
All organic salts are liquids of brown color.
IR spectra were recorded by using an ALPHA FT-
IR spectrometer (Bruker,USA) using KBr tablets.
Surface tension () values were measured by Du
Nouy ring method using a KSV Sigma 702 tensiometer
(Finland).
Specific electroconductivity (κ) values were deter-
mined by “Anion-4120” electroconductometer (Rus-
sia).
Resuls and Their Discussion
The reaction between hexadecylamine and propyl-
ene oxide is illustrated as following:
4 Norwegian Journal of development of the International Science No 27/2019
where n=m+k.
In order to obtain organic salts, in the second step, propoxy derivative of the hexadecylamine was reacted
with different monocarboxylic aliphatic acids as following:
where R is CH3, C10H21 and C17H35. The products are
defined as from Salt 1 to Salt 3, respectively to the
radicals of the carboxylic acids.
Structure and composition of the final products
were analyzed by using IR spectroscopy. The IR-
spectra are given in Figure 1.
By examining IR spectra, it was deduced that ab-
sorption bands at 3327.87 cm-1
in the first spectrum,
3349.88 cm-1
in the second spectrum and 3197.23 cm-1
in the third one represent OH valent vibration bands. C-
H valent vibration bands of CH3, CH2 and CH groups
are observed at 2922.29-2853.09 cm-1
in the first spec-
trum, 2920.31-2851.84 cm-1
in the second spectrum and
at 2916.63-2849.55 cm-1
in the third spectrum.
Norwegian Journal of development of the International Science No 27/2019 5
Figure 1. IR spectra of the synthesized salts: a) salt 1; b) salt 2; c) salt 3
C-H deformational vibrations bands exist at
1459.23-1375.59 cm-1
, 1460.89-1378.84 cm-1
,
1462.47-1379.02 cm-1
, while C-N valent vibration
bands are at 1259.26 cm-1
, 1284.93 cm-1
and 1285.88
cm-1
, respectively in the first, second and third spectra.
C-O valent vibrations band of C-OH group can be de-
fined at 1052.22 cm-1
in Salt 1 spectrum, 1047.67 cm-1
in Salt 2 and 1088.02 cm-1
in Salt 3 spectra. (CH2)x
“pendulum”vibrations bands exist at 720.89 cm-1
in the
first spectrum, 722.57 cm-1
in the second spectrum and
723.91 cm-1
in the third spectrum.
Surface tension data of Salts 1, 2 and 3 were de-
termined at temperatures 25, 24 and 26o
C, respectively.
 versus concentration (c) plots of the components are
given in Figure 2.
Figure 2. Surface tension at the water-air border versus concentration plots of the salts
0
20
40
60
80
0 0,0005 0,001 0,0015 0,002 0,0025
,mN/m
c, mol/l
Salt 1
Salt 2
Salt 3
6 Norwegian Journal of development of the International Science No 27/2019
Bu using these plots of the salts, characteristic pa-
rameters of the surface activity can be determined. Crit-
ical micelle concentrations (CMC) of the salts were
found out as 5.28*10-5
, 1.78*10-5
and 3.58*10-5
mol/l
respectively. Additionally, CMC, surface pressure
(πCMC), C20 (the concentration for reduction of  by 20
mN/m), adsorption efficiency (𝑝𝐶20 = −𝑙𝑜𝑔𝐶20) as
well as CMC/C20 values of the all salts were determined
according to [3] and given in Table 1.
Maximum surface excess concentration-Г 𝑚𝑎𝑥 val-
ues were calculated from the following equation:
Г 𝑚𝑎𝑥 = −
1
𝑛 ∗ 𝑅 ∗ 𝑇
∗ lim
𝑐→𝑐 𝐶𝑀𝐶
𝑑 
𝑑 𝑙𝑛𝑐
where R is universal gas constant (R=8.3145
C/mol*K) and T is absolute temperature. The value of
n was taken as 2 because 2 ions are formed by dissoci-
ation of the salts.
The minimum value of the area for one surfactant
molecule of the salts at the water-air border (Amin) were
determined by the given equation
𝐴 𝑚𝑖𝑛 =
1016
𝑁𝐴 × Г 𝑚𝑎𝑥
and tabulated in Table 1.
Table 1
Surface activity parameters of the synthesized surface-active salts
Surfactant
CMC×105
(mol/L)
CMC
(mN/m)
πCMC
(mN/m)
C20×105
(mol/L)
CMC/
C20
pC20
Γmax×1010
(mol/cm2
)
Amin×102
(nm2
)
Salt 1 5.28 32.16 39.84 0.57 9.26 5.24 2.97 55.9
Salt 2 1.78 31.37 40.63 1.07 1.66 4.97 5.41 30.71
Salt 3 3.58 28.23 43.77 0.99 3.62 5.01 2.48 66.85
Specific electrical conductivity dependence on
concentration was studied for the first salt-at 24.8o
C,
for the second salt-at 26.4o
C and for the third salt-at
26.2o
C. Isotherms of the specific electrical conductivity
were plotted and given in Figure 3:
Figure 3. Specific electrical conductivity versus concentration plots of the obtained salts
Slopes of the straight line before (S1) and after (S2)
CMC value of each salt were determined. Such thermo-
dynamic properties as Gibbs free energy of micelliza-
tion (ΔGmic) and Gibbs free energy of adsorption (ΔGad)
values were calculated according to the following equa-
tions:
𝛥𝐺 𝑚𝑖𝑐 = (2 − α) × 𝑅 × 𝑇 × ln(𝐶𝑀𝐶)
𝛥𝐺 𝑎𝑑 = (2 − α) × 𝑅 × 𝑇 × ln(𝐶𝑀𝐶) − 0.6023
× 𝜋 𝐶𝑀𝐶 × 𝐴 𝐶𝑀𝐶
where 𝐴 𝐶𝑀𝐶 is surface area of the one surfactant
molecule at the interface in terms of Å2
.
Table 2
Specific electrical conductivity parameters and thermodynamic parameters of micellization and adsorption
of the obtained salts
Surfactant α Β ΔGmic, kJ/mol ΔGad, kJ/mol
Salt 1 0.29 0.71 -41.73 -43.07
Salt 2 0.03 0.97 -53.38 -54.13
Salt 3 0.02 0.98 -46.82 -48.58
As is seen, the ΔGad values are more negative than
the ΔGmic values which points out to preference of the
adsorption of the surfactants rather than the micelle for-
mation.
In order to identify petrocollecting property of the
surface-active salts, unthinned reagents, 5% wt. aque-
ous and ethanolic solutions of the salts were separately
added to the water with thin petroleum layer. Thin layer
(~0.17 mm) of Pirallahi (oil field near Baku, Azerbai-
jan) petroleum was formed on the surface of 40 ml dis-
tilled, tap and sea (the Caspian) water in Petri dishes.
For each salt, maximum duration of the petrocollecting
action and maximum petrocollecting coefficient-K at
room temperature were determined and given in Table
3. The value of “K” is derived as the ratio of the area of
the surface of initial petroleum film and the area of the
0
5
10
15
20
25
30
35
40
45
0 0,0005 0,001 0,0015 0,002 0,0025
κ,µS/sm
c, mol/l
Salt 1
Salt 2
Salt 3
Norwegian Journal of development of the International Science No 27/2019 7
surface of the petroleum spot formed under the action
of the salts.
Table 3
Maximum duration of petrocollecting action and maximum petrocollecting coefficients of the synthesized salts
Surfactant State of surfactant
Duration,
hours
Maximum petrocollecting coefficient
Distilled water Tap water Sea water
Salt 1
Unthinned reagent
191
39.06 36.80 36.80
5% wt. aqueous solution 33.97 33.97 33.97
5% wt. ethanolic solution 31.54 31.54 29.44
Salt 2
Unthinned reagent
191
33.97 33.97 31.54
5% wt. aqueous solution 33.97 31.54 31.54
5% wt. ethanolic solution 33.97 31.54 30.45
Salt 3
Unthinned reagent
167
22.08 11.04 11.04
5% wt. aqueous solution 12.62 9.81 9.81
5% wt. ethanolic solution 14.72 9.81 9.81
As becomes evident from the obtained data, Salt 1
is more effective than the other two salts. In the sea and
fresh waters, Kmax for Salt 1 is 36.8, whereas for the
other two salts this index is lower. Aqueous solution of
Salt 1 is more effective than its ethanolic solution.
REFERENCES:
1. H.H.Humbatov, R.A.Dashdiyev, Z.H.Asadov
et.al. Chemical Reagents and Petroleum Production,
Baku:Elm, 2001,448 p.
2. Asadov Z.H. Azerbaijan oil industry. 2009,
№2, p. 60-65.
3. Asadov Z., Ahmadova G., Rahimov R. Et al.
Synthesis and Properties of Quaternary Ammonium
Surfactants Based on Alkylamine, Propylene Oxide
and 2-Chloroethanol, Journal of Surfactants and
Detergents. 2018,21. p.247-254.
4. Asadov Z., Zarbaliyeva I., Zargarova S.
Propoxylation of Aliphatic Amines by Propylene
Oxide, Journal of Chemical Problems, 2017,1. p.44-50.
5. S.H.Zargarova, I.A.Zarbaliyeva,
R.A.Rahimov, Z.H.Asadov. Synthesis and Study of
Surface-Active Salts Based on Propoxy Derivatives of
Dodecylamine and Monocarboxylic Aliphatic Acids.
Proceedings of International Scientific-Practical
Conference on Petroleum and Gas Industry,
Almetyevsk (Russia), 2018, p.587-589.
6. M.J.Rosen. Surfactants and Interfacial
Phenomena, 3rd
Edn.New York: John Wiley and Sons,
Inc-2004,444p.
ACETYLTHIOUREA LEACHING GOLD FROM TAILS OF FLOTATION DEPOSIT DZHIKIKRUT
Kholov Kh.
Assistant of the name of V.I.Nikitin Institute of Chemistry,
Academy of Sciences of the Republic Tajikistan
Samikhov Sh.
Doctor of Technical Sciences,
The Leading sciences of the name of V.I.Nikitin Institute of Chemistry,
Academy of Sciences of the Republic Tajikistan
АЦЕТИЛТИОМОЧЕВИННОЕ ВЫЩЕЛАЧИВАНИЕ ЗОЛОТА ИЗ ХВОСТОВ ФЛОТАЦИИ
МЕСТОРОЖДЕНИЯ ДЖИЖИКРУТ
Холов Х.И.
аспирант Института химии им. В.И. Никитина
Академии наук Республики Таджикистан
Самихов Ш.Р.
доктор технических наук, главный научный сотрудник
Института химии им. В.И. Никитина
Академии наук Республики Таджикистан
Abstract
The presented results of the study on gold leaching proved that after pretreatment of tailings, acetylthiourea
satisfactorily leaches gold from them.
Аннотация
Представленные результаты исследования по выщелачиванию золота доказывают, что после предва-
рительной обработки хвостов ацетилтиомочевина удовлетворительно выщелачивает из них золото.
8 Norwegian Journal of development of the International Science No 27/2019
Keywords: acetylthiourea, leaching, trivalent ferrous sulfate, sulfuric acid, gold-antimony-mercury ore, gold-
containing solution.
Ключевые слова: ацетилтиомочевина, выщелачивание, трёхвалентный сульфат железа, серная кис-
лота, золото-сурьмяно-ртутная руда, золотосодержащий раствор.
Для выщелачивания золота из золотосодержа-
щих руд широко используется цианирование. Во-
преки преимуществу перед другими растворите-
лями, высокая токсичность цианидов вынуждает
искать альтернативные растворители золота, удо-
влетворяющие ужесточенным экологическим тре-
бованиям. Целая группа нецианистых растворите-
лей – тиомочевина (тиокарбамид), гидросульфиды,
хлор, тиосульфаты натрия и аммония, бром и соли
гуминовых кислот изучены в Иргиредмет [1, с.415].
Тиокарбамидное выщелачивание, произведен-
ное тем или иным способом, – перспективный гид-
рометаллургический процесс извлечения золота [2,
с.141]. Для проведения этого процесса необходимо
применять эффективный окислитель, способный
переводить металлическое золото в ионное состоя-
ние и поддерживать низкие значения pН с целью
предохранения от разложения золотосодержащего
комплекса. Это достигается путем введения в про-
цесс серной кислоты и сульфата трёхвалентного
железа.
Для снижения расхода тиокарбамида предва-
рительно окисляют сульфиды железа, сурьмы, меди
в кислой среде гидроксидом железа [3, с.182]. Из
тиокарбамидных растворов золото осаждают це-
ментацией свинцом, цинком, алюминием, сорбцией
на активных углях, щелочами, электролизом.
В промышленном масштабе тиомочевина при-
меняется лишь на предприятиях с очень богатым
концентратом, что оправдывает затраты на реагент.
В России в итоге испытаний на опытных установ-
ках выявлены неисправность способа: длитель-
ность операции закисления, высокий расход кис-
лоты, обогащение продуктивных растворов эле-
ментами примесями и др. [3, с.189].
Эксплуатационные затраты при тиокарбамид-
ном выщелачивании в целом примерно на 25 %
меньше, чем для цианирования за счет существенно
(более чем в три раза) меньших затрат на обезвре-
живание промышленных стоков. Нами в лаборатор-
ных условиях проведены исследования по ацетил-
тиомочевинному выщелачиванию золота из хво-
стов флотации нижнего горизонта месторождения
Джижикрут [5, с.534].
Исследования в области выщелачивания кон-
центрата проводились в стеклянных стаканах емко-
стью 500 мл, использовавшейся стеклянной гидро-
мешалки с двумя лопастями. Навеска концентрата,
заваливавшегося в склянку, прибавлявшийся рас-
твор ацетилтиомочевины и серная кислота, давав-
ший окислитель трёхвалентного сульфата железа и
производилось размешивание в течение определён-
ного промежутка времени. После 2,4,6,8 часов по-
сле начала исследование мешалку останавливали, и
производился отбор аликвоты для определения рН
и концентрации золота. В растворах золото опреде-
лялось методом атомно-абсорбционной спектро-
скопии. Испытание проводилась в 1 %-ном рас-
творе ацетилтиомочевинны при 1,38 % серной кис-
лоты и 0,5 % трёхвалентного сульфата железа. Дли-
тельность время опытов 8 часов, рН среды - 6,0.
Золото в раствор, в данных условиях, переходило в
незначительных количествах (таблица 1). Оче-
видно из таблицы 1 и рисунка 1, за 8 часов в раствор
выщелачивается Au – 20,8%.
Ради улучшения процесса ацетилтиомочевин-
ного выщелачивания пробы хвостов флотации под-
вергались обжигу при температурах 200 – 600 °С в
продление 2 часов. В абразии и при обжигании про-
исходит вскрытие упорных золото - сульфидных
концентратов, в то же время минералы пирит и ар-
сенопирит окисляются, по этой причине происхо-
дит вскрытие содержащегося в них золота.
Таблица 1
Извлечение золота благодаря ацетилтиомочевинному выщелачиванию хвостов флотации нижнего
горизонта Джижикрутского месторождения
Время,
ч
Правило опыта Концентра-
ция Au в
растворе,
мг/л
Извлечение
Au, %руда, г вода,
мл
CH3CONH
CSNH2,
г
H2SO4
(конц.),
мл.
Fe2(SO4)3,
г
pН
Нач. 100 200 2 1,5 1,5
2 1,0 5,8 0,165 19,4
4 6,1 0,174 20,5
6 5,8 0,175 20,6
8 5,8 0,177 20,8
Norwegian Journal of development of the International Science No 27/2019 9
Рис.1. Выщелачивание золота при температурах 200 0
С
Окисление пирита начинается возле темпера-
туры 450 – 500 °С. Процесс протекает с образова-
нием как промежуточного продукта пирротина.
FeS2 + O2 = FeS + SO2, окисляется до магнетита
3FeS + 5O2 = Fe3O4 + 3SO2 и через некоторое время
до гематита 2Fe3O4 + 1
/2O2 = 3Fe2O3. В таблицах 2,3
и рисунках 2,3 показаны испытанные результаты.
Очевидно из таблицы и рисунка, за исключе-
нием кислотной обработки хвостов, обожженных
благодаря температуре обжига 200 0
С в раствор пе-
реходило 19,5 % золота, а около 400 °C с последу-
ющим выщелачиваем ацетилтиомочевинной в рас-
твор переходит всего лишь 21,6 % золота. Увеличе-
ние температуры обжига до 600 °С способствует
тому, что извлечение золота повышается до 45,2 %.
Только после обжига при температуре 600 °С
вследствие рН = 1,2 в раствор переходило 83,3 % с
дальнейшей кислотной обработкой спустя 8 часов
извлечение золота в раствор из хвостов составило
86,1 %.
Таблица 2
Извлечение золота благодаря ацетилтиомочевинному выщелачиванию хвостов флотации нижнего
горизонта Джижикрутского месторождения
Время,
ч
Правило опыта Концен-
трация Au
в рас-
творе,мг/л
Извлече-
ние Au,%
руда,
г
вода,
мл
CH3CONHCSNH2,
г
H2SO4
(конц.),
мл.
Fe2(SO4)3,
г
pН
нач. 100 200 2 1 1
2 5,8 0,165 19,4
4 6,1 0,174 20,5
6 5,8 0,175 20,6
8 5,8 0,177 20,8
Хвосты флотации после обжига при 200 0
С
2 5,3 0,144 16,9
4 5,3 0,152 17,9
6 5,8 0,168 19,8
8 5,8 0,166 19,5
Хвосты флотации после обжига при 400 0
С
2 5,6 0,162 19,0
4 5,9 0,173 20,3
6 6,2 0,181 21,3
8 6,0 0,184 21,6
Хвосты флотации после обжига при 600 0
С
2 6,2 0,338 39,8
4 6,4 0,379 44,6
6 6,2 0,381 44,8
8 6,8 0,384 45,2
10 Norwegian Journal of development of the International Science No 27/2019
Рис.2. Зависимость извлечения золота от времени при температурах 200 до 600 0
С
Таблица 3
Извлечение золота благодаря ацетилтиомочевинному выщелачиванию хвостов флотации позже об-
жига при температуре 600 0
С
Время,
ч
Правило опыта Концен-
трация Au
в растворе,
мг/л
Извлече-
ние Au, %
руда,
г
вода,
мл
CH3CONHCSNH2,
г
H2SO4
(конц.),
мл.
Fe2(SO4)3,
г
pН
нач. 100 200 2 20 1
2 1,6 0,631 74,2
4 1,4 0,663 78,0
6 1,4 0,700 82,3
8 1,2 0,708 83,3
Хвосты флотации после обжига при 600 0
С + обработка серной кислотой
2 2,4 0,648 76,2
4 2,8 0,685 80,6
6 2,6 0,730 85,9
8 2,6 0,732 86,1
В ходе исследования ацетилтиомочевинного
выщелачивания золота из руд выявлены следую-
щие его преимущества как растворителя по сравне-
нию с цианированием: низкая токсичность, исклю-
чение из схемы необходимости обезвреживания
стоков, отвалов и т.д.; высокая скорость растворе-
ния металлов, меньшее воздействие на компо-
ненты-примеси, слагающие руду; меньший расход
реагента на единицу массы руды; более полное из-
влечение золота в цикле выщелачивания, особенно
при наличии в рудах его сульфидных форм; воз-
можность осуществления комбинации отдельных
стадий выщелачивания, направленных на улучше-
ние технологических показателей (предваритель-
ная кислотная обработка, окисление сульфидов или
совмещение этих двух процессов); простая схема
регенерации растворителя путем очистки от приме-
сей (известкование), позволяющая осуществить
бессточную гидрометаллургическую технологию.
Norwegian Journal of development of the International Science No 27/2019 11
Рис.3. Зависимость извлечения золота из хвостов флотации до и после обжига при температурах 600
0
С и с обработке серной кислотой
Следовательно, использование ацетилтиомо-
чевины с целью выщелачивания золота из руд и
хвостов флотации рентабельно. Помимо того, с
применением ацетилтиомочевины извлечение зо-
лота во много раз выше, чем при цианировании.
СПИСОК ЛИТЕРАТУРЫ:
1. Лодейщиков В.В. Технология извлечения
золота и серебра из упорных руд. В 2-х т. – Иркутск:
ОАО «Иргиредмет», 1999, 786 с.
2. Захаров Б.А., Меретуков М.А. Золото:
упорные руды. - М.: Руда и Металлы, 2013, 450 с.
3. Самихов Ш.Р., Зинченко З.А., Бобомуро-
дов О.М. Изучение условий и разработка техноло-
гии тиомочевинного выщелачивания золота и сере-
бра из руды месторождения Чоре. – Доклады АН. -
Душанбе, 2013 -т. 56, № 4 с. 181-184.
4. Лодейщиков В.В., Панченко А.Ф. Основы
технологии извлечения золота и сурьмы из ком-
плексных руд. – Интенсификация процессов обога-
щения минерального сырья. – М.: Наука, 1981, с.
189-193.
5. Самихов Ш.Р., Холов Х.И., Зинченко З. А.
Технология обогащения руд нижних горизонтов
Джижикрутского месторождения. – Доклады АН
РТ – 2017. Том 60. - №10 с. 533-538.
UDC 541.64:544.032:577.12
EFFECT OF PLANT ENVIRONMENT ON DECOMPOSITION OF BIODEGRADABLE MATERIALS
BASED ON POLY-3-HYDROXYBUTYRATE AND POLYLACTIDE
Shibryaeva L.
D. Sc., Prof., Leading researcher
N. M. Emanuel Institute of Biochemical Physics, Russian Academy Sciences
Federal Scientific Agroengineering Center VIM
Tertyshnaya Yu.
Ph.D., Senior Researcher
N. M. Emanuel Institute of Biochemical Physics, Russian Academy Sciences
Federal Scientific Agroengineering Center VIM
Solovova Yu.
Ph. D., Junior researcher
N. M. Emanuel Institute of Biochemical Physics, Russian Academy Sciences
Levina N.
Senior researcher
Federal Scientific Agroengineering Center VIM
Zhalnin E.
D.Eng, Prof., Head of Laboratory
Federal Scientific Agroengineering Center VIM
12 Norwegian Journal of development of the International Science No 27/2019
Abstract
Samples of nonwoven material from biodegradable polymers poly-3-hydroxybutyrate and polylactide used
as carriers of wheat seeds, accelerate their germination compared to control. The nonwoven fabric is prepared by
electroforming the fibers in organic solvents. Paper filters are used as a control. The influence of germinated seeds
on the thermal parameters of melting and physical and mechanical properties of biodegradable polymer carriers is
shown. It is established that there is a relationship between the destruction of the polymer material and the rate of
germination of seeds, as well as the development of the root system of plants. It is shown that the destruction of
polymers proceeds through several mechanisms, which depend on the stage of seed germination. At the initial
stage, the mechanism of hydrolytic degradation and enzymatic catalysis of polymers is considered. The process of
polymer destruction by mechanical destruction under the influence of growing roots is discussed at the stage of
root system development. The development of the root system leads to the appearance of microcracks, their fusion
with the formation of holes in the polymer material. The kinetics and mechanism of destruction of the seed carrier
polymer and the growth rate of the root system depend on the nature and structure of the polymer. Nature
determines the direction of crack germination in the polymer carrier for polylactide - along its surface, for poly-z-
hydroxybutyrate in volume.
Keywords: wheat seeds, biodegradable polymers, nonwoven materials, poly-3-hydroxybutyrate, polylactide,
destruction.
Introduction
The most important task of the agro-industrial
complex of any contry is the introduction of innovative
technologies aimed at increasing the yield of
agricultural crops and the creation of environmentally
friendly products. These technologies are based on non-
traditional methods of cultivation and storage of
agricultural products. Among them are the technologies
of mulching soil, pelleting seeds of onions, carrots,
tomatoes and other vegetables, based on the use of film
materials from biodegradable compositions based on
natural and synthetic polymers [1-4]. Recently, the
technology of planting seeds in the soil on a polymer
tape has been developed for grain crops in Russia [5,6].
The use of the tape involves the provision of
environmentally friendly conditions for germination of
seeds of grain crops, their protection from the effects of
pathogenic systems, the creation of a microclimate
favorable for seed germination and plant development.
This technology is extremely important for seed
farms. It is supposed that the tapes filled with seeds
together with mineral fertilizers can create conditions
for production of elite grades of grain crops. The main
requirement for the materials used for the manufacture
of tapes-carriers of seeds, is their ability to provide
conditions for the life of crops. First of all, such
materials, in contact with germinating seeds and plants,
should not only not violate the mechanism of their
development, but also stimulate these processes. The
materials must be predisposed to degrade under the
action of biological fluids, oxygen, UV- radiation with
a high speed with the formation of environmentally
friendly products, not contaminating the soil. At the
same time, it must have mechanical parameters that can
ensure the planting of seeds in the carrier tape into the
soil with the help of agricultural machinery. Today
there is a problem of creation of a material for tapes –
carriers of seeds capable to solve objectives.
The most suitable materials that can meet the
requirements are biopolymers based on oxy-derived
fatty acids, the so - called polyhydroxyalkanoates, the
main advantages of which are their high physical and
mechanical properties and environmental friendliness
[7]. Poly-3-hydroxybutyrate (PHB) and polylactide
(PLA) were used for agricultural purposes in [8-10].
Properties of these polymers provide their wide
application in agricultural and food industry, medicine
and biology [11-16]. They undergo biodegradation in
enzymatic catalysis under the action of bacteria and
fungi [12]. It is important for the metabolism of plant
cells that the stresses arising in polymer chains, causing
the decay of bonds, initiate radical chain processes of
oxidation of macromolecules [13]. The decomposition
products of these biodegradable polymers are carbon
dioxide and water. However, to date, there are no
studies of the processes of biodegradation of polymers
under the influence of the environment which created
by germinating seeds and developing plants.
The aim of the work was to establish patterns of
biodegradation of polymer materials based on PHB and
PLA under the influence of germinating wheat seeds.
Experimental part
Poly-3-hydroxybutyrate (PHB) of German firm
"Biomer" with molecular weight Mw=2,5×105 g/mol
in the form of fine powder, d = 1,248 g/cm3;
polylactide (PLA) of brand 4032D manufactured by
"Nature Works" (USA) with Mw=1,7×105 g/mol in the
form of granules, with d =1,27 g/cm3
; mixtures of PHB
with synthetic nitrile rubber (SNR) were used in the
work. SNR of Russian production with 28 wt.% of
nitrile groups, with the Mooney viscosity at 100o
C - 45
c. u., PHB-SNR mixtures contained 30 wt.% rubber's
were used.
Samples in the form of extruded films and
nonwoven material were investigated. Films with
thickness of 80 - 120 mcm was obtained by pressing
PLA at 195-200, PHB at 150-175о
С, with subsequent
slow cooling. The nonwoven material was prepared
from nanofibers obtained by electroforming by
exposure to an electric voltage of 10-60 kV to an
electrically charged jet of 6% solution of each of the
polymers in chloroform or in a mixture of chloroform
with dichloroethane in a ratio of 80:20 wt.% arising
from the capillary nozzle [17,18].
We studied the germination, germination of seeds,
growth and development of seedlings of spring wheat
varieties "Athena" (Triticum aestivum) harvest in 2015
(Krasnodar region) in the laboratory. For seed
Norwegian Journal of development of the International Science No 27/2019 13
germination, they were placed in Petri dishes of 50
seeds in accordance with GOST 12038-84 [19] on
moistened pads made of paper filters or polymer
material. Samples were filled with distilled water so
that moisture covered the seeds. Germinating seeds
were kept in a thermostat at a temperature of 20±1 ° C,
maintaining a constant level of humidity.
As a reference to monitor the germination of seeds
and development of plants on the polymeric samples
was used a substrate of disinfected paper filters brand
Blue ribbon FM without impurities on the other 2642-
001-68085491-2011. After 1,2,3 days, the number of
sprouted seeds was determined as a percentage in each
batch of samples taken for analysis (at least 5 samples).
Seed germination energy was defined as the percentage
of normally sprouted seeds in the first three days.
Germination-on the seventh day. During 14 days the
dynamics of growth of wheat roots and seedlings was
analyzed.
Experimental data were processed using
dispersion and correlation analysis according to the
programs "AGROS-2.02". The accuracy of
determining the germination parameters is not less than
1.5%.
The thermophysical characteristics of polymer
materials were determined using a differential scanning
calorimeter of the company ("Netzsch", Germany,
model DSC-204 F1) at a heating rate of 10 deg/min in
the temperature range of 30-200 ° C in argon current. A
portion of the sample was varied in the range of 2÷8 mg
using DSC received values of the heats and melting
points of PHB and PLA.
To accurately determine the parameters,
corrections were introduced into the recorded values
for the parameters of the melting peak indium (with the
temperature and heat of melting of Tm=156.7°C and
Hm=28.58 J/g). The heat of fusion was determined by
the crystallinity of the PHB and PLA ratio
=(ΔHm / ΔH*m) × 100%, where ΔHm - the heat
absorbed during the melting of the sample per unit mass
of pure polymer, ∆H*m - the specific heat of fusion of
crystals of PHB and PLA is 90 [20] and 106 J/g [21],
respectively.
The accuracy of the melting temperature of the Tm
is±1 ° C. Standard deviations of experimental areas of
melting peaks of different samples (at least 10 samples)
were within 10%.
The surfaces of the polymer samples, the structure
and thickness of the fibers of the nonwoven material
were investigated using an optical microscope Axio
with a thermal imager Z2m, Carl Zeiss with software;
with 50×, 200×, 500× magnification in both transmitted
and reflected light.
Physico-mechanical parameters, including tensile
stress (F), relative elongation (ε), breaking length (L) of
PHB and PLA samples were determined on a tensile
testing machine RM-3-1 according to GOST
25.061065-72. The speed of movement of the lower
clamp is set 45±5 mm/min. Samples of seeds grown on
substrates during 9 and 14 days were dried, cleaned
from the root system of plants and cut in the form of
blades. The parameters were calculated by load –
elongation curves. To obtain each value, 2 batches
containing at least ten samples were used. Standard
deviations of experimental parameters were within ±
20%.
The parameters of water absorption of a solution
of amylase, extracted from the seeds and roots of wheat,
nonwoven material and polymeric films of native seeds
was determined according to GOST 4650-80 [22]. The
tests were carried out on square-shaped samples of
~30×30 mm in size by at least 3 for each material.
Before determining the parameters, the samples were
dried at (50±2)°C for (24±1) hours, then cooled in the
desiccator above the desiccant at (23±2) ° C. After
cooling, the samples were weighed for 5 minutes.
After that, the samples were placed in vessels with
distilled water and amylase extract. On 1 cm2
of the
sample surface there was at least 10 cm3
of liquid. The
liquid with the sample placed in it was stirred by
rotating the vessel at least once a day. When
determining the maximum degree of swelling in the
water (to equilibrium), the equilibrium was considered
achieved if the difference between the mass of the
sample determined with an interval of 24 hours did not
exceed 0.1 %. After that, the samples were removed
from the vessels and placed on a clean filter and
removed moisture from the surface. Then weighed on
electronic scales. The degree of water absorption and
absorption of amylase solution was calculated by the
formula:
α = (m -mo)/ mo . 100%, where mo – the initial
mass of the sample, m – the mass of the sample after
saturation with water or a solution of amylase during
time .
IR spectroscopy and optical microscopy were used
to control the filling of amylase films. IR spectra were
obtained using a Fourier transform spectrometer of the
company Perkin-Elmer.
Results and discussion
Important indicators of the possibility of using
biodegradable materials for the technology of growing
wheat as substrate – carriers of seeds is the ability of
the material to destruct in contact with germinating
seeds and at the same time affect the rate of germination
of seeds and the development of various organs of the
plant. In order to establish the feasibility of using of
materials, based on poly-3-hydroxybutyrate and
polylactid, for carriers of seeds, were carried out
laboratory studies of dynamics of germination of wheat
seeds on their surface in an aqueous medium (in Petri
dishes).
We used samples of extruded films and nonwoven
material made of polymers PHB, PLA, and mixtures of
PHB-SNR structures. In the course of the work the
regularities of changes in thermophysical and physico-
mechanical parameters of the above samples under the
influence of germinating seeds and developing root
system with seedlings were studied. With the aim of
establishing a relationship between the kinetics of
destruction of the polymer and the dynamics of plant
development parameters of germination, energy of
germination and biometric parameters of wheat germ
that grew on the samples of polymer materials were
compared with similar parameters obtained for seeds
14 Norwegian Journal of development of the International Science No 27/2019
germinated on paper filters, performing the role of
control samples. The results are presented in table. 1.
Table. 1. Indicators of germination and biometric
parameters of wheat seed seedlings of the "Athena"
variety (Triticum aestivum).
Comparison of the parameters of the germination
and biometric parameters of seedlings of wheat seeds
(table. 1) demonstrates noticeable differences in the
indicators of seeds sprouted on polymer carriers from
the control samples. When comparing samples of
different polymeric carriers, differences in the
germination rates of seeds germinating on them were
found. Moreover, these differences depend on the
chemical composition and structure of the substrate. On
substrates of nonwovens seed germination and
development of the root system on them are
significantly accelerated compared to the control
substrates of paper filters, while the pressed films seed
germination slows and plant growth is inhibited (table.
1). At the study of the dynamics of seed germination on
carriers of nonwovens was found to increase the effect
of the impact on the seeds in the transition from the
stage of ontogenesis with the formation of the root to
the stage of growth and development of the root system
and seedlings (table. 2). If at the stage of ontogenesis
there is a tendency to increase the quantitative
parameters (germination and energy of seed
germination) in comparison with the control, then at the
stage of growth there is a significant increase in
biometric indicators (table. 2).
Table 2. The dynamics of germination of wheat
seeds on different carriers
Figure 1 shows a significant increase of
differences between the parameters of seed seedlings,
root system and wheat germ grown on the surface of
the paper filter and of nonwoven material PHB with
increased time of germination of seeds. As can be seen,
the rate of development of wheat on a biodegradable
polymer substrate is accelerating, which can be
explained by the factor of initiation of growth processes
on the part of the polymer.
a b
c d
e f
Fig. 1. Photos of samples of wheat seeds which sprouted in Petri dishes on the surfaces of substrates – carriers
of seeds from paper filter (a, с, e) and nonwoven material from PHB (b,d,f) in the aqueous medium for 2 (a,b), 4
(с,d) and 7 (e,f) days
Norwegian Journal of development of the International Science No 27/2019 15
The study of changes in polymer substrates –
carriers in the process of germination of seeds and
seedlings in the dynamics of the latter showed that
developing plants are not indifferent to the polymer
substrates and have a significant impact on the
structural, physical and mechanical parameters of the
latter. The germination of seeds and the development of
seedlings on a sample of polymer material lead to its
destruction, as evidenced by the decrease in mass. The
results of the study of reducing the mass of samples in
the process of destruction as a result of contact with
germinating seeds are presented in table 3.
Table. 3. The mass of samples of initial films and
after germination of seeds in them
As can be seen from table 3, the samples of
nonwoven material from PHB and PLA, being in direct
contact with the plants for 9 days decreased in weight
by 1.4 and 2.2 times respectively. It is important to note
that the samples has been dried and prepared for out
weighing to obtain these results. It was taken into
account that after the experiment some part of the plant
roots was directly in the material, however, even with
its mass significantly decreased compared to the mass
of the original sample (table. 3). The development of
the root system on polymer carriers causes changes in
their physical and mechanical properties. On the tensile
testing machine were tested samples of nonwoven
material PHB and PLA, the original and after the
experiment, in the continuation of which the material
was in direct contact with the plant. The analysis of the
obtained data showed that after germination of seeds in
PHB the values of relative elongation, maximum load
and breaking length are significantly reduced, in
polylactide with a significant drop in the index of
relative elongation, the maximum load and breaking
length are increased by ~ 2.5-3 and 6 times,
respectively (table. 4). I.e. is detected the dependence
of the nature of the impact of growing roots on the
polymeric carriers from their chemical structure.
Table. 4. Physical and mechanical characteristics
of seed substrates of nonwoven PGB, PLA initial and
after germination of wheat seeds in them.
Figure 2 shows photos of destructive samples of
nonwovens PHB and PLA exposed to the root system
and seedlings during wheat growth for more than 14
days. Figure shows a different picture of the destruction
of polymers. Based on the picture of destruction of
PHB and PLA, shown in Fig. 2 and data in table. 4, it
can be assumed that the observed difference in the
change in mechanical parameters of PLA and PHB
samples under the action of developing plants is due to
different mechanisms of biodegradation of these
polymers. It is possible that a significant increase in the
maximum load and breaking length in the PLA is due
to the influence of the reinforcing layer that strengthens
the matrix, which arose from the undeleted root
residues due to the development of the root system
along the surface of the carrier (Fig. 2). At the same
time, the roots of PHB germination are carried out in
the depth of the material, creating a “hole” in the
polymer matrix (Fig.2).
Fig. 2. Photographs of the samples of substrates of seeds from nonwoven material PHB (a) and PLA (b) with
germinated in them root systems of wheat.
Change of thermophysical parameters of samples
of nonwoven material under the influence of
germinated seeds was investigated by DSC method.
The melting thermograms of crystallites were
compared for the initial films – seed carriers before
their planting and after germination of plants and
substrates exposed to the growing root system. Fig. 3
presents an example of endothermic melting peaks for
nonwoven PHB materials and the PLA before and after
germination of seeds in them.
16 Norwegian Journal of development of the International Science No 27/2019
Fig.3. Endotherms of melting of samples of nonwovens PHB (1,2) and PLA (3,4,5), before (1,3) and after (2,4,5)
germination of seeds in them within 9 (2,4) and 14 (5) days.
Endotherms characterizing the melting of
crystallites of the initial carriers of PHB and PLA have
one peak in the temperature range 150-190o
C with a
maximum temperature (Tmax) equal to 172.8°C in PHB
and 166°C in PLA.
The nature of the change in the shape of the peaks
in the samples after germinate the seeds were depends
on the nature and structure of the polymer material and
the time of seed germination (Fig. 3). The analysis of
melting endotherms was carried out for 9 and 14 days
of seed germination. The peak of melting of PHB is
shifted to the low-temperature region by several
degrees and a low-melting shoulder appears after 9
days (Fig. 3). Changes in the shape of PLA melting
peaks depend on the time of root germination to a
greater extent than that of PHB. For example, after 9
days of seed germination, there is a shift in the melting
peak Tmax in the high-temperature region with the
appearance of a low-melting shoulder nearby with Tmax
of the initial sample (Fig. 3). After 14 days, the entire
melting peak shifts to the low-melting region (Fig. 3).
The change in the forms of melting peaks of PHB and
PLA is accompanied by a drop in the melting heat,
hence the degree of crystallinity (table. 5). The shift in
melting temperatures and the decrease in the degree of
crystallinity indicate the destruction of crystal
structures.
Table. 5. Thermophysical parameters of polymer
samples of the substrates - carriers of the seed from
nonwoven material
From the difference of the magnitudes of the fall
of the heat of fusion of the crystallites in samples of
non-woven materials PHB, PLA, prepared from
solutions in chloroform and mixtures of chloroform-
dichloroethane (table. 5), the influence of the substrate
structure on the seed germination rate is clearly
observed (table. 1,2). Thus, the degree of crystallinity
in samples of PHB prepared from CHF and CHF with
EDC after germination of seeds in them is reduced by
1.8 and 1.1 times, respectively, in the sample of PLA
from CHF by 1.1 times, in the sample mixture of PHB+
SCN-by 3-3. 5 times (table. 5). The greatest drop in the
degree of crystallinity of the substrate corresponds to
the largest mass and length of roots and seedlings
(table. 1) and the highest seed germination index (table.
2).
To the question about the mechanism of
degradation of polymeric substrates under the
action of growth of seeds of wheat
Norwegian Journal of development of the International Science No 27/2019 17
An important task, the solution of which depends
on the use of the studied materials as seed carriers, is to
establish the mechanism and kinetics of biodegradation
of the carrier under the action of germinating seeds and
developing plants. Based on the literature data on the
physiology of plants, as well as from the above results
obtained in our work, it can be argued that the
biodegradation of the polymers, which occurring in
contact with germinating seeds, is not described by a
single mechanism. The latter can vary depending on the
stage of plant growth and the parameters of the
polymer-seed carrier.
At the ontogenesis stage, the determining factor of
germination of seeds, is the rate of grain swelling and
water supply to the embryo [23,24]. Germination of
seeds on the surface of the polymer carrier will
inevitably depend on the ability of the carrier to provide
the embryo with water, hence the process of swelling
of the polymer in contact with the grain and the rate of
diffusion of water through the polymer to its surface.
At this stage, the beginning of the destruction of
polymer substrates may be due to swelling and caused
by hydrolysis of polymer macromolecules.
Biodegradation of polyethers based on polylactide and
polyhydroxybutyrate is mainly carried out by
hydrolysis of ether bonds by reaction:
-COO- + H2O —> -COOH + HO-
On the other hand, it is known that in the course of
biochemical processes developing in germinating
wheat grains, enzymes are formed, the main of which
is amylase. Amylase can be run from the seed through
the aleuronic layer into an aqueous medium in contact
with the polymer. In this case, at the stage of seed
germination with the formation of the embryos and root
system, in contact with the surface of the polymer
carrier in an aqueous medium, the conditions for the
reaction of enzymatic hydrolysis of the polymer. As is
known for the reaction of the formation of intracellular
enzymes that lead to the growth of roots and seedlings,
requires a lot of energy. This energy can be obtained by
the destruction of biodegradable polymers. Because the
observed acceleration of seed germination on substrates
of nonwoven materials PHB and PLA compared to the
control samples, it is possible to hypothesize about the
existence of the mutual influence of the speed of seed
germination and the decomposition of the polymeric
substrate and its nature.
The essence of this effect is that the polymers in
contact with the seeds in the aqueous medium,
subjected to enzymatic hydrolysis under the action of
amylase released from the seeds, are energy "food" for
the development of biochemical processes of formation
of enzymes that stimulate the germination of plant
seeds. To test the above hypothesis, the kinetics of
hydrolysis of polymer carriers in distilled water and
aqueous amylase solution was studied. Amylase
solutions were prepared by extraction of the enzyme
from swollen seeds.
Kinetic curves were obtained that characterize the
swelling of polymer samples of pressed PHB film and
nonwovens PHB and PLA and hydrolytic degradation
under the action of water, as well as enzymatic
decomposition in an aqueous solution of amylase.
These curves are shown in Fig. 4.
Fig.4. Kinetic curves of swelling of samples of nonwoven material PHB (1), PLA (2), extruded films PHB (3) in
distilled water, sorption and hydrolytic degradation of nonwoven materials PHB (4) and PLA (5) in the water
extract of amylase and the curve of swelling of wheat seeds in water (6).T=22o
C.
As can be seen from the figure within the selected
time interval, the kinetic swelling curves of the studied
samples have a typical form of the process with an
accelerated initial stage and a stationary site. The
kinetics of swelling of nonwoven material in water is
described by the equation [22]:
, (1)
, (2)
где k - the rate constant of swelling
α -
18 Norwegian Journal of development of the International Science No 27/2019
αmax – maximum degree of swelling,
From these curves it can be seen that the studied
samples differ in the values of the swelling rates at the
initial site and the maximum degrees of swelling
max max of the pressed film PHB is significantly
lower (40- max
of the nonwoven material of PHB is greater (380%)
than PLA (240%).
The swelling rate constants (k) for the initial
stages of water saturation (3 days) of polymer samples,
were estimated by equations (1) and (2), were equal
~0.088, ~0.1136, ~0.1144 h-1
for PHB films,
nonwovens PHB and PLA, respectively. For
comparison, in Fig. 4 the kinetic curve of swelling of
seeds in the aqueous medium (curve 6) to the stage of
their germination is presented. This curve includes the
stage of seed swelling, passing into the stage
germination with the appearance of roots and seedlings
for 3 days. The constant swelling rate (before the
emergence of seedlings), estimated for seeds similar to
polymer substrates, was ~0.12 h-1
, which is within the
same range with the data obtained for polymer
substrates of nonwoven materials.
Since the water diffusion coefficient of nonwoven
PHB material (density ρ = 0,12 - 0,21 g/cm3
DH2O = 4.0
10-10
cm2
/s ) is higher than from the extruded film PHB
(DH2O is 3.6.10-11
cm2
/s [25,26]) may be to conclude
that for a friable structural organization of the
nonwoven material is characteristic not only a greater
degree of swelling of seeds, but and it increase of rate
of diffusion of water towards its embryo, this is
determines the growth rate germination of seed in
contact with nonwoven material.
Kinetic curves presented for non-woven fibers of
PHB and PLA after their stand in an aqueous extract of
wheat seeds containing amylase (Fig. 4, curves 4.5),
demonstrate a significant effect of the enzyme. (The
appearance of amylase in the aqueous medium was
recorded by changing the pH of the aqueous medium
with swollen grain and its UV- spectrum). In place of
hydrolytic destruction is enzymatic hydrolysis. It is
important that these curves can distinguish the initial
stage characteristic of the swelling process in water
with increasing sample mass. After the first stage, there
is a loss of polymer mass, indicating enzymatic
hydrolysis (curves 4,5). A particularly high rate of mass
loss is observed in the sample of PHB (curve 5), in PLA
this rate is lower (curve 4).
When comparing the kinetic curve of swelling of
seeds in the aqueous medium (Fig. 4, curve 6) with a
curve of the enzymatic hydrolysis of non-woven fibers
(especially for PHB (Fig. 4, curve 4) reveals that the
time corresponding to the beginning of the selection of
the enzyme and the emergence of seedlings in the
swelling of the seed (~3 days) corresponds to the
beginning of the fall weight of the polymer on the curve
of enzymatic hydrolysis. The penetration of water into
the seed substrate material, leading to hydrolysis in
water and enzymatic decomposition in the enzyme
solution, initiates violations in its structure.
This follows from the comparison of the
thermophysical parameters of melting of the crystal
structures of the studied samples of the original
nonwoven materials PHB and PLA, with the treated
aqueous medium and enzyme extract of seeds obtained
by DSC. The melting endotherms of polymer samples,
after swelling in water for 144 hours (previously dried
at room temperature to a constant weight), show a shift
of the melting peak by several degrees towards high
temperatures, with the appearance of a low-melting
shoulder (Fig. 5).
This is due to the recrystallization of the polymer,
which occurs under the influence of water molecules
localized in the amorphous regions. From the melting
endotherms of samples hydrolyzed in amylase, a
significant destruction of the crystal structure of the
polymer follows. This is evidenced by the shift of the
maximum melting peak for PHB and PLA towards low
temperatures ~to 10 degree (Fig. 5). At the same time,
the melting heat reduction reaches 9% (table. 6). It is
important to note that a significant decrease in the
melting temperature, indicating the enrichment of the
crystalline structures of low-melting fraction of
crystallites characteristic of enzymatic hydrolysis.
Fig.5. Endotherms of melting samples of nonwoven PHB material: initial (1) exposed to aqueous medium (2)
and amylase extract with pH=11 (3).
Norwegian Journal of development of the International Science No 27/2019 19
Table. 6. The thermophysical parameters of
samples of nonwoven material PHB, treated with water
and extract with amylase and enzymes
It is known that the rate of hydrolysis is different
for materials with different chemical and physical
structures and depends on the presence of crystalline
regions in the polymer, access to which is difficult.
Hydrolysis can occur mainly on the surface of the
polymer material, and in its volume.
Perhaps the hydrolytic destruction of nonwoven
PHB and PLA material in amylase affects their
molecular structure in different ways. Usually for
polylactide hydrolysis acceleration in the depth of the
product occurs in the case of pH drop caused by acidic
degradation products. However, in our case, the
observed decrease in the rate of falling weight of PLA
in the medium of wheat seed extract containing
amylase, the process takes place in an alkaline medium
at pH = 11. Saturation of polymer films with amylase
was controlled by IR spectra. Visible decrease in the
rate of PLA degradation, observed from the enzymatic
hydrolysis curves (Fig.4, curves 4.5), can be explained
by the surface process (erosion). A sharp drop in the
mass of PHB indicates that the destruction process
develops in the volume of the polymer.
The fact of different localization of hydrolysis of
PHB and PLA confirms the comparison of the pictures
presented on microphotographs (Fig. 6), demonstrating
the surface of the samples of nonwoven materials of
PHB and PLA, obtained after filling with amylase from
the extract and after the last destructive processes of
enzymatic hydrolysis (Fig. 6). In the PLA sample,
small cracks and small depressions are observed along
the entire surface. In PHB-clearly expressed significant
depressions and pits, locally distributed in separate
zones on the surface of the polymer (Fig. 6).
Fig.6. Microphotographs of samples of nonwoven material PHB (a, b) and PLA (c, d), initial (a, c) and sub-
jected to enzymatic hydrolysis for 6 days under the action of an aqueous extract of amylase from germinating
seeds (b, d).
It should be noted such experimental results as:
first, the quantitative relations between the rate
constants of swelling of polymers and seeds in water
(Fig. 4, curves 1,2,4,6); secondly, the ratio between the
time of amylase release into the aqueous medium and
the beginning of seed germination and the time
corresponding to the process of enzymatic hydrolysis
of the polymer substrate material (Fig.4 curves 4,6);
third, the destruction of the crystal structures of the
studied polymer samples under the action of enzymatic
hydrolysis (Fig. 5); fourth, the data optical microscopy
of the surface, reflecting the nature of the enzymatic
hydrolysis of PHB and PLA in the seed extract (Fig. 6).
Apparently, these results confirm the possibility of
implementing the above hypothesis about the nature of
the stimulating effect obtained from polymer carriers at
the initial stage of seed germination as an effect caused
by enzymatic hydrolysis of the polymer substrate.
The possibility of the enzymatic hydrolysis of the
carrier during the germination of seeds on it was
evaluated by the effect on the nonwovens of PHB
aqueous extract of enzymes isolated from sprouted
roots. The extract was prepared from the mass of roots
grown after 9 days of seed germination. The melting
endotherms of PHB obtained after treatment with this
extract for several days demonstrated the same
20 Norwegian Journal of development of the International Science No 27/2019
character of changes in the polymer melting parameters
that was observed in the sample treated with amylase
from seed extract. The differences were in a greater
drop in heat and melting temperature - a greater shift of
the peak to the low-temperature region (table. 6).
Comparison of melting parameters of polymeric
carriers of seeds on the example of samples of
nonwoven PHB material exposed to seed germination
before the stage of root formation, with samples
exposed to enzymatic hydrolysis, indicates the
presence of polymer destruction in both cases.
However, the mechanisms of destruction are different.
If the of seed carrier, under the action of the root
system, there is mainly a significant drop in
crystallinity, i.e. amorphization of the polymer (table.
5), that the sample, which subjected to hydrolysis,
changes the structure of the crystalline regions without
a significant drop in their volume. For example,
samples of PHB with sprouted roots reduce the melting
temperature of crystallites (Tmax) to ~4o
C with a
significant drop in the degree of crystallinity (from ~47
to 70%) (table 5). In the sample subjected to enzymatic
hydrolysis, the decrease in Tmax reaches 8-10o
C. At the
same time, the degree of crystallinity varies by 9%
(table. 6).
Comparison of the curves of temperature
dependences for the degree of transformation of
crystalline structures into melt during melting of
nonwoven material PHB demonstrates the differences
in shape of curves in samples, subjected to enzymatic
hydrolysis and in the samples after formations in them
of the root system ( Fig. 7). Obviously, this is due to
different laws of melting of PHB, due to different
mechanisms of destruction of polymeric materials.
Fig.7. Curves of the temperature dependence of the degree of conversion the crystallites PHB into the melt dur-
ing melting of the nonwoven material PHB for initial sample (1), for sample after germination into it of the root
system (2) for samples which were subjected to a water environment (3) and amylase (4)
Apparently, the contribution into the destruction
of the polymeric substrates - carriers of the enzymatic
hydrolysis process, can be come to light at the stage of
ontogenesis, at the stage of formation and development
of the root system this mechanism is replaced by
another. Analysis of photographs of the samples of
substrates seeds obtained for the stage of root formation
and growth (presented in Fig. 2) indicate the evident
destruction of the polymer under the influence of
germinated this roots. In this case, the roots of the plant
create mechanical stresses in the polymer, which there
are creation cracks, their fusion, leading to the
formation of through holes. Indeed, the pictures (Fig. 2
a, b) which are demonstrate surface of seed carriers,
obtained on the 9 the day, show the evident cracks and
holes in the polymer (Fig. 2). It is important to note that
in the samples of PHB are dominated by transverse
holes, while in the PLA they are longitudinal, parallel
to the surface of the film.
The pattern of destruction of PHB and PLA
corresponds to the nature of the root system. In the first
polymer roots germinate in a perpendicular direction to
the surface of the film, in the second – parallel to the
surface. It can be assumed that the direction of growth
and development of the root system in the nonwoven
biopolymer material associated with the initiation of
seed germination by enzymatic hydrolysis of the
polymer carrier, developing on the surface or directed
to the volume of the polymer. In turn, this may depend
on the structure of the nonwoven material, the structure
of their crystallites and amorphous regions, on the
nature of the polymer, which determines the
mechanism of its biodegradation [13, 27].
Besides the mechanisms of destruction of the
polymer carrier of seeds by enzymatic hydrolysis and
mechanical action, another mechanism of destruction is
possible. Another process in which the biodegradable
polymer carrier of seeds can destroy, affecting the stage
Norwegian Journal of development of the International Science No 27/2019 21
of plant growth is the ability of the polymer to
participate in radical reactions [28]. Mechanical
destruction that occurs in the polymer under the action
of roots may rouse the appearance of free radicals.
In addition, the main direction of biochemical
processes in the germinating seed, which is enzymatic
hydrolysis of starch and lipids, which is in the mass of
the seed, may be accompanied by the formation of an
excess of free radicals that can destroy cell structures,
therefore, lead to cell death.
Contact of germinating seeds with
macromolecules of the polymer substrate through an
aqueous medium can lead to the interaction of free
radicals, which may pick out from the seed into water,
with the functional bonds of the macromolecules
contacting with it.
Resulting in the reaction of transfer of free valence
(r*) from the cell molecule (MH) into the polymer
macromolecule (RH), which is convert the kinetic
chains of oxidation of cell molecules, protects them
from destruction, i.e., the polymer carrier in relation to
the cells acts as an antioxidant. At the same time, the
oxidation process can be initiated in polymer
macromolecules by the following reaction [28]:
MH → r*
RH+ r* —> R* + rH
Thus, oxidation of the polymer carrier
significantly accelerates the destruction of its
amorphous regions. It can be thought that the ability of
the polymer matrix to break off the kinetic chains of the
oxidative process in cells promotes the development of
anabolic reactions of cell growth and, therefore, can
accelerate the growth of the root system and plant
germs. It is explains the acceleration of the
development of wheat sprouts at a more advanced stage
of plant growth on the substrate PHB (Fig. 1).
Ability to assess the contribution of enzymatic
hydrolysis, mechanical degradation and radical process
into summary process of biodegradation of polymer
carriers during seed germination may by definite by
comparing the energy parameters of melting crystal
structures of polymers. That estimated calculation was
made for nonwoven material PHB.
Known high sensitivity of wheat seeds to the
energy effects, causing the flow of biochemical
processes, in particular enzymatic processes. Reducing
the energy barrier causing the participation of enzymes
can occur due to the decomposition of macromolecules
or decomposition of crystal structures.
In this work, the activation energy of crystallite
melting Ea was estimated. For this purpose, the
Kissinger equation (Kissinger) was used for
thermograms obtained by heating the sample at a
constant rate [29]. The equation is based on the
dependence of the fixed temperature on the polymer
heating rate:
Еa = [RТ1Т2 /(Т2 -Т1)] ln(V2/V1), (3)
where Еa – activation energy,
R- Universal gas constant,
Т1, Т2 – temperature in K, corresponding to heating
rates of the sample V1 и V2.
Ea was determined with the help of equation (3). It
were establish the change in the maximum melting
point (Tmax), its shift according at the speed of heating
in the range of 4 to 16 degrees/min, defined with respect
to the standard (In). The obtained values Ea. are
presented in table. 6. As can be seen from this table,
enzymatic hydrolysis of PHB leads to a significant drop
in the activation energy of crystallite melting. The low
value of Ea indicates a high degree of defectiveness of
the structure of the crystallites as a consequence of their
destruction. It is important to emphasize the fact that Ea
of the crystallites of PHB treated with root enzymes are
lower than those treated with amylase (table 6). The
value of Ea in a sample of PHB with sprouted roots is
also reduced compared to the original polymer, and is
close to the sample treated with water, which may
indicate the process of polymer destruction occurring
under the action of sprouted seeds, as a process mainly
occurring in amorphous areas.
Conclusion
Analysis of the dynamics of changes in the
parameters of wheat growth on polymer substrates
shows that the process of seed germination and growth
of the root system of the plant is autocatalytic and
correlates with the destruction of the polymer material.
Based on the data obtained, it follows that the
processes of destruction of polymeric materials
stimulate seed germination and plant growth. In turn,
the processes of seed germination are initiated
degradation of polymers.
Destruction of the polymeric carrier of wheat
seeds from biodegradable material includes several
mechanisms depending on the stage of plant
development. Comparison of processes of destruction
of materials from PHB and PLA, occurring in the
absence of contact with the plant, shows the
acceleration of the destruction of the polymer under the
action of extract of amylase, isolated from the seeds and
enzymes isolated from the root system of wheat.
Comparison of the melting parameters of the
samples of polymeric substrates after enzymatic
hydrolysis with parameters of the samples obtained
after germination of the root system lets make a guess
that the effect of polymeric carrier on the rate of
germination of wheat seeds is depend on process of
enzymatic hydrolysis of the substrate at the stage of
ontogenesis and radical processes of
mechanodestruction and oxidation of the polymer at the
stage of growth and development of plant.
The nonwoven materials PHB and PLA are most
suitable in quality carriers of seeds. Ability of these
polymers to show the stimulating action to the plant
seeds depends on structural parameters, which define
the ability to swell and chemical stability in an aqueous
solution of enzymes and activity to oxidative
destruction. Due to the different location of amorphous
and crystalline regions in the fibers of nonwoven PLA
compared with PHB changes the direction of growth
the root system.
22 Norwegian Journal of development of the International Science No 27/2019
Table 1.
Indicators of germination and biometric parameters of wheat seed seedlings of the "Athena" variety (Triticum
aestivum).
Sample
№
Characteristics of the
sample-substrate in a
Petri dish
**Seed
germina-
tion, %
** Massa, g *Energy
germinations
seeds', %
**Length
root, cm
**Height
plants, cmFull plant root
1
2
3
4
5
6
7
Control (filter paper)
PLA extruded film
PLA non-woven material
PHB extruded film
PHB non-woven material
PHB+SCN pressed film
PHB+SCN nonwoven
material
86±2
88±2
92±2
90±2
96±2
96±2
96±2
0.156±0.008
0.114±0.008
0.184±0.01
0.124±0.008
0.178±0.01
0.160±0.01
0.196±0.01
0.035±0.002
0.020±0.001
0.054±0.003
0.028±0.002
0.050±0.003
0.048±0.002
0.050±0.003
80±2
50±5
70±2
55±5
96±1
94±1
94±1
7.8±1.0
5.6±1.5
12.0±2.0
8.2±1.8
10.4±1.5
9.4±2.0
9.8±1.0
117±2
118±5
125±5
120±5
135±5
125±5
138±5
Note: *the germination energy, defined on the 3 day.
** data obtained on the 7th day of seed germination
Table 2.
The dynamics of germination of wheat seeds on different carriers
Characteristics of the
sample material of the
substrate seed
The solvent
from which
the obtained
nonwoven
material
The number of germinated seeds. Germination
index, GIon the
1-st
day
on the
2-nd
day
on the
3-rd
day
on the
4-th
day
on the
7-th
day
Control
PLA extruded film
PLA non-woven material
PHB extruded film
PHB non-woven material
PHB non-woven material
PHB+SCN nonwoven
fabric
PHB+SCN nonwoven
fabric
-
-
CHF
-
CHF
CHF + EDC
CHF
CHF + EDC
0
0
0
0
0
0
0-2
2-3
5-7
0
7-10
3-5
5-7
6-7
46-47
10-46
35-40
5-8
25-27
5-7
45-48
45-48
47-48
45-49
43-44
25-30
47-48
24-26
47-49
48-49
47-49
47-49
43-45
35-40
47-48
39-41
47-49
48-49
47-50
47-50
0.60-0.62
0.40-0.41
0.63-0.65
0.44-0.46
0.69-0.72
0.70-0.71
0.81-0.82
0.72-0.81
Table 3.
The mass of samples of initial films and after germination of seeds in them
Characteristics of the samples sample series № Sample mass, g
PHB non-woven material initial
PHB after seed germination
PLA non-woven material source
PLA after seed germination
1
2
1
2
1
2
1
2
0.0189±0.002
0.0182±0.002
0.0102±0.002
0.0098±0.001
0.0494±0.005
0.0445±0.005
0.022±0.003
0.0197±0.002
Table 4.
Physical and mechanical characteristics of seed substrates of nonwoven PHB, PLA initial and after germination
of wheat seeds in them
Characteristics of the
samples
sample
series №
Relative
elongation, %
The maximum
load, H
Breaking length, m
PHB nonwoven material
initial
PHB after seed germination
PLA nonwoven
initial material
PLA after seed germination
1-2
1-2
1-2
1-2
2.4-3.9
1.0-1.1
30.2-86.1
6.6-16.3
0.9-1.4
0.5-0.9
1.3-1.6
3.7-4.0
406.3-454.7
201.0-364.7
175.1-194.3
1073.0-1129.0
Note: measurement Error of physical and mechanical parameters, ±20%
Norwegian Journal of development of the International Science No 27/2019 23
Table 5.
Thermophysical parameters of polymer samples of the substrates - carriers of the seed from nonwoven material*
Characteristics of the sample
material of the substrate seed
Temperature, Т, о
си Hm,
J/g
χ, % , day
Тм 1 Tmax Тм 2
PHB (CHF) initial
after seed germination
PHB (CHF + EDC) initial
after seed germination
PHB+SCN (CHF) source
after seed germination
PHB+SCN (CHF + EDC)
initial
after seed germination
PLA (CHF) initial
after seed germination
After seed germination
156.0
158.0
160.0
156.0
162.0
153.0
147.0
159.0
152.0
156.0
152.0
175.0
173.5
172.8
169.8
173.0
170.0
172.0
170.0
168.9
170.2+ shoulder 164.0
162.5+ shoulder 160.0
190.0
184.0
185.0
180.0
180.0
179.0
177.0
179.0
174.0
174.0
168.0
61.3
34.1
65.2
59.7
62.8
20.8
61.2
17.6
41.0
36.0
35.0
68.1
37.9
72.4
66.3
69.7
23.1
68.0
19.5
38.6
34.0
33.0
0
9
0
9
0
9
0
9
0
9
14
*Note: Tm1 - initial temperature of the melting peak, Tmax. Temperature at the maximum peak of melting, Tm2
- final melting peak temperature, Hm. - melting heat, χ is the degree of crystallinity, the time of seed
germination.
Table 6.
The thermophysical parameters of samples of nonwoven material PHB, treated with water and extract with am-
ylase and enzymes
Characteristicss
samples
The temperature
of the maximum
melting peak
Tmax, 0
C
The heat of fusion
H, J/g
Crystallinity de-
gree
, %
Activation energy of
melting of crystallites
of PHB Ea, kJ/mol
PHB nonwoven initial mate-
rial
PHB after germination of
seeds with the appearance of
roots (more than 9 days)
PHB nonwoven material after
saturation with water
PHB nonwoven material
after saturation with amylase
from an aqueous seed extract
PHB nonwoven material after
the saturation of the enzyme
from the aqueous extract of
the roots
172.0-174.0
170.0-174.0
170.0+ shoulder
164
164.0+ shoulder
160.0
160.0+ shoulder
157.0
62.9
33.2
60.0
57.1
51.0
69.9
36.9
66.7
63.4
56.7
500±20
470±30
450±60
209±30
169±20
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hydroxybutyrate) and poly(lactic acid): A Review”. //
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10. Shibryaeva L.S., Tertyshnaya Yu.V., Pal'mina
D.D., Levina N.S. “The Biodegraded Polymers as
Materials for Sowing of Grain Crops Seeds” // Rus.:
Cel`skochozyastvennye mashiny (Agricultural
machinery and technology). - 2015. - N 6. - P.14-18.
11. Tertyshnaya Yu.V., Shibryaeva L.S.
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Scale Application in Industry of Russia”// Rus.:
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12. Araujo W.F., Botrel T.A. “Influence of CO2
applied with the irrigation water and plastic mulch on
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- N 2. - Р. 216-221.
13. Tertyshnaya Y.V., Shibryaeva L.S., Ol`khov
A.A. “Thermal Oxidation and Degradation of Poly-3-
hydroxybutyrate Nonwoven Materials” // Russian
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- P.498-503.
14. Bonartsev A.P., Bonartseva G.A., Artsis M.I.,
Iordanskii A.L., Zaikov G.E. “Biodegradation and
medical application of microbial poly(3-
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DOI:10.1080/15421406.2012.635549
15. Ol'khov A.A, Sklyanchuk E.D., Abbasov T.A.
et al. “Regeneration Potential of a New Tendon Implant
Made of Polyhydroxybutyrate Nanofibres” // Rus.:
Technologii zhivyich sistem (Technology of living
systems). - 2015. - V. 12. - N 2. - P. 3-11.
16. Shishatskaya E.I., Kamendov I.V.,
Starosvetsky S.I., et al. “An in vivo study of
osteoplastic properties of resorbable poly-3-
hydroxybutyrate in models of segmental osteotomy and
chronic Osteomyelitis” // Artificial Cells,
Nanomedicine, and Biotechnology. - 2014. - N 40. - P.
344-355.
17. GOST 12038-84. “Seeds of agricultural crops.
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18. Filatov Yu. N. “Electroforming of fibrous
materials (EFF- process)” / Editor V. N. Kirichenko.
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19. Matveev, A. T., Afanasov I. M. “Obtaining
nanofibers method of electroforming” / Textbook for
students. Moscow: MGU, 2010. - 83 p.
20. Ol`khov A.A., Vlasov C.V., Shibryaeva L.S.
et al. “Structural Features of LDPE-Poly(3-
hydroxybutyrate) Blends”// Polymer Science. Ser. A. -
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21. Sarasua J.R., Lopez A.A., Balerdi P., Maiza I.
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23. Metlitsky, L. V. Rus: Biochimiya na strazhe
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24. Obroucheva N.V., Sinkevich I.A., Lityagina
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25. Iordanskii A.L., Kamaev P.P. “The Effect of
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26. Kamaev P.P., Aliev I.I., Iordanskii A.L.,
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Norwegian Journal of development of the International Science No 27/2019 25
MEDICAL SCIENCES
УДК 616.993:078-08.084
EVALUATION OF DEGREE OF IMMUNE DYSFUNCTION AS OF CYTOKINES IN PATIENTS
WITH LIVER ECHINOCOCCOSIS
Bodnya K.
Kharkiv Medical Academy of Postgraduate Education, Ministry of Health of Ukraine
Velieva T.
Kharkiv Medical Academy of Postgraduate Education, Ministry of Health of Ukraine
Bodnya I.
Kharkiv Medical Academy of Postgraduate Education, Ministry of Health of Ukraine
ОЦІНКА СТУПЕНЯ ІМУННОЇ ДИСФУНКЦІЇ ЗА СТАНОМ ЦИТОКІНОВОЇ СИСТЕМИ У
ХВОРИХ НА ЕХІНОКОКОЗ ПЕЧІНКИ
Бодня К.І.
Харківська медична академія післядипломної освіти МОЗ України
Велієва Т.А.
Харківська медична академія післядипломної освіти МОЗ України
Бодня І.П.
Харківська медична академія післядипломної освіти МОЗ України
Abstract
The paper presents the results of the study of the current situation in echinococcosis, he characteristic of the
basic diagnostic methods is given and the treatment-diagnostic algorithm is optimized, which improves the results
of treatment. 73 patients with echinococcosis and cytokines IL-1β, IL-1 Ra, IL-4, IL-8, IFN-γ were examined іn
order to evaluate the state of the cytokine system.
Анотація
В роботі представлені результати вивчення сучасної ситуації з ехінококозу, дана характеристика
основних методів діагностики та оптимізовано діагностичний алгоритм, що покращує результати лікування.
З метою оцінки стану цитокінової системи у хворих на ехінококоз обстежено 73 особи та були досліджені
цитокіни IL-1β, IL-1 Ra, IL-4, IL-8, IFN-γ.
Keywords: echinococcosis, diagnostics, cytocine IL-1β, IL-1 Ra, IL-4, IL-8, IFN-γ.
Ключові слова: ехінококоз, діагностика, цитокіни IL-1β, IL-1 Ra, IL-4, IL-8, IFN-γ.
Ехінококоз печінки тяжке паразитарне захво-
рювання, яке зустрічається у жителів всієї земної
кулі, але має різну тенденцію до поширення в різ-
них географічних регіонах. Однак необхідно відзна-
чити, що офіційно наведені дані не завжди відобража-
ють дійсну частоту захворюваності. Так, в Чилі, що є
одним з осередків ехінококозу, в результаті проведе-
ного узагальненого аналізу офіційних даних, публіка-
цій в літературі і безпосередньої роботи в госпіталях
встановлено, що ехінококоз зустрічається у 8,5-11,4
на кожні 100 тисяч населення, що в 4 рази перевищує
офіційні дані [1]. Такая же ситуация наблюдается и в
Украине: по официальным данным захворюваність на
ехінококоз превышает данные официальной статис-
тики.
Серед країн СНД ендемічними регіонами є Ре-
спубліки Середньої Азії, Молдова і деякі регіони
Росії. Захворюваність на ехінококоз в Турк-
меністані, Молдові, Киргизстані становить 3,8-5,5
на 100 тисяч населення [2, 3]. В Узбекистані рівень
ураження на ехінококоз варіює в середньому від 6
до 9 осіб на 100 тисяч населення. Кількість
щорічних операцій в цій республіці становить 1-1,5
тисяч з летальністю 2,5-7% і більше [3]. Незважаючи
на доброякісну природу, ехінококоз є однією з про-
блемних областей хірургічної гепатології, через часті
ускладнення і тривалі терміни стаціонарного ліку-
вання. Будучи крайовою патологією, ехінококоз довгі
роки залишається однією з головних проблем цен-
трально-азіатського регіону [4, 5].
Територія України є осередком напруженості
епізоотичних процесів, до яких відноситься і ехіноко-
коз, частота якого має стійку тенденцію до збільшення.
Однокамерний ехінокок паразитує в личинковій
стадії у проміжного хазяїна − більш ніж у 60 видів тра-
воїдних і всеїдних копитних тварин, а у статевозрілій
стадії − у 15 видів м'ясоїдних, включаючи вовка, ша-
кала, які є остаточними хазяями [6, 7]. Існуючі труд-
нощі ранньої і диференціальної діагностики, обумов-
лені тривалим безсимптомним перебігом хвороби, пі-
знім зверненням хворих за медичною допомогою,
коли вже спостерігаються ускладнені форми ехіноко-
козу печінки, а киста досягає великих розмірів, ство-
рюють тактичні і технічні складнощі при проведенні
оперативного втручання [8, 9, 10]. Найбільш частими
є хронічні ускладнення: нагноєння паразитарної ки-
сти, яке зустрічається у 18,4-49% випадків, звапніння
фіброзної капсули – у 4,8-18,1% осіб [11, 12].
Частота гострих ускладнень ехінококозу, таких
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
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Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
Norwegian Journal of development of the International Science №27 part 1
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Norwegian Journal of development of the International Science №27 part 1

  • 1. №27/2019 Norwegian Journal of development of the International Science ISSN 3453-9875 VOL.1 It was established in November 2016 with support from the Norwegian Academy of Science. DESCRIPTION The Scientific journal “Norwegian Journal of development of the International Science” is issued 12 times a year and is a scientific publication on topical problems of science. Editor in chief – Karin Kristiansen (University of Oslo, Norway) The assistant of theeditor in chief – Olof Hansen  James Smith (University of Birmingham, UK)  Kristian Nilsen (University Centre in Svalbard, Norway)  Arne Jensen (Norwegian University of Science and Technology, Norway)  Sander Svein (University of Tromsø, Norway)  Lena Meyer (University of Gothenburg, Sweden)  Hans Rasmussen (University of Southern Denmark, Denmark)  Chantal Girard (ESC Rennes School of Business, France)  Ann Claes (University of Groningen, Netherlands)  Ingrid Karlsen (University of Oslo, Norway)  Terje Gruterson (Norwegian Institute of Public Health, Norway)  Sander Langfjord (University Hospital, Norway)  Fredrik Mardosas (Oslo and Akershus University College, Norway)  Emil Berger (Ministry of Agriculture and Food, Norway)  Sofie Olsen (BioFokus, Norway)  Rolf Ulrich Becker (University of Duisburg-Essen, Germany)  Lutz Jäncke (University of Zürich, Switzerland)  Elizabeth Davies (University of Glasgow, UK)  Chan Jiang(Peking University, China) and other independent experts 1000 copies Norwegian Journal of development of the International Science Iduns gate 4A, 0178, Oslo, Norway email: publish@njd-iscience.com site: http://www.njd-iscience.com
  • 2. CONTENT CHEMICAL SCIENCES Asadov Z.,Zargarova S.,Zarbaliyeva I. Rahimov R.,Huseynova S. SYNTHESIS AND STUDY OF SURFACE-ACTIVE SALTS BASED ON PROPOXY DERIVATIVES OF HEXADECYLAMINE AND MONOCARBOXYLIC ALIPHATIC ACIDS.........................................................3 Kholov Kh.,Samikhov Sh. ACETYLTHIOUREA LEACHING GOLD FROM TAILS OF FLOTATION DEPOSIT DZHIKIKRUT...............................7 Shibryaeva L.,Tertyshnaya Yu., Solovova Yu.Levina N.,Zhalnin E. EFFECT OF PLANT ENVIRONMENT ON DECOMPOSITION OF BIODEGRADABLE MATERIALS BASED ON POLY-3-HYDROXYBUTYRATE AND POLYLACTIDE.............................................................11 MEDICAL SCIENCES Bodnya K.,Velieva T.,Bodnya I. EVALUATION OF DEGREE OF IMMUNE DYSFUNCTION AS OF CYTOKINES IN PATIENTS WITH LIVER ECHINOCOCCOSIS .....................................................25 Gaponov K. PECULIARITIES OF VITALITY IN ALCOHOL-ADDICTED PATIENTS WITH DIFFERENT LEVELS OF PSYCHOSOCIAL STRESS.......................................................................33 Pozdnyakova M.,Izmaylova T. MALE INFERTILITY AS A MEDICAL AND SOCIAL PROBLEM ..................................................................40 Nikolaeva I.,Radkevich L. GENETIC AND ENVIRONMENTAL FACTORS FOR THYROID CANCER......................................................42 Oprya Ye. SYSTEM OF COMPLEX REHABILITATION OF PATIENTS WITH SHYSOFRENIA IN VIEW OF SOMATIC COMORBIDITY ...........................................................46 PHISICAL SCIENCES Etkin V. ENERGODYNAMIC THEORY OF GRAVITATION AND LEVITATION ...............................................................51 Gladyshev G. HIERARCHICAL TERMODYNAMICS RULES THE WORLD TO THE EXTENT OF ITS APPLICABILITY ......................60
  • 3. Norwegian Journal of development of the International Science No 27/2019 3 CHEMICAL SCIENCES SYNTHESIS AND STUDY OF SURFACE-ACTIVE SALTS BASED ON PROPOXY DERIVATIVES OF HEXADECYLAMINE AND MONOCARBOXYLIC ALIPHATIC ACIDS Asadov Z. Doctor of Chemical Sciences, professor, corresponding member of Azerbaijan National Academy of Science; head of laboratory of surfactants of Institute of Petrochemical Processes (IPCP) Zargarova S. Senior instructor of Baku Higher Oil School, post-graduate researcher of laboratory of surfactants of IPCP Zarbaliyeva I. PhD (Chemistry), associate professor, leading researcher of laboratory of surfactants of IPCP Rahimov R. Doctor of Chemical Sciences, associate professor, chief researcher of laboratory of surfactants of IPCP Huseynova S. Scientific researcher of laboratory of surfactants of IPCP Baku Azerbaijan Abstract Salts of the oligomeric propoxy derivatives of hexadecylamine with several organic acids were synthesized. Structure and composition of the salts were confirmed by using IR spectroscopy. Surface tension and electrocon- ductivity properties of the oligomers were examined and corresponding main parameters of the salts were calcu- lated. Moreover, petrocollecting properties of these salts were determined and maximum values of petrocollecting coefficients were calculated. Keywords: hexadecylamine, propoxy derivative, salt, surfactant, petrocollecting Introduction The increasing demand to crude oil and products of its refining results in ecological instability and dis- balance. In order to improve ecological balance of the nature, surfactants are used in industry including oil production and refining [1,2]. Thin oil layers on the surface of the water become one of such ecological problems which may occur during transportation of crude oil and its refining products. According to the literature, higher aliphatic amines may be used for synthesis of surface-active compounds [3-5]. In a given study, surfactants are obtained from hexadecylamine, propylene oxide and monocarboxylic aliphatic acids. Main physical-chemi- cal properties of the new surfactants including colloi- dal-chemical ones were determined in order to apply them as petrocollecting agents. Experimental Hexadecylamine was a product of “Alfa Aesar GmbH & Co KG” firm (Germany) of purity > 98%. Propylene oxide was a product “Organic Synthe- sis” factory (Sumgayit, Azerbaijan) of 99.97-99.98% purity. Monocarboxylic aliphatic acids were “analytically pure” grade products of Novocherkassk Plant of Syn- thetic Products (Russia). Potassium hydroxide was used as “analytically pure” product of “Chemapol” firm (Czech Republic). Oligomer of hexadecylamine and propylene oxide was synthesized at 140-150o C for 13-14 hours in an au- toclave made of stainless steel and equipped with a reg- ulator of temperature. In the given reaction, potassium hydroxide was used as a catalyst. In the second step, propoxy derivative of the hexadecylamine reacted with different monocarboxylic aliphatic acids at 50-60o C for 5-6 hours in order to obtain organic salts. All organic salts are liquids of brown color. IR spectra were recorded by using an ALPHA FT- IR spectrometer (Bruker,USA) using KBr tablets. Surface tension () values were measured by Du Nouy ring method using a KSV Sigma 702 tensiometer (Finland). Specific electroconductivity (κ) values were deter- mined by “Anion-4120” electroconductometer (Rus- sia). Resuls and Their Discussion The reaction between hexadecylamine and propyl- ene oxide is illustrated as following:
  • 4. 4 Norwegian Journal of development of the International Science No 27/2019 where n=m+k. In order to obtain organic salts, in the second step, propoxy derivative of the hexadecylamine was reacted with different monocarboxylic aliphatic acids as following: where R is CH3, C10H21 and C17H35. The products are defined as from Salt 1 to Salt 3, respectively to the radicals of the carboxylic acids. Structure and composition of the final products were analyzed by using IR spectroscopy. The IR- spectra are given in Figure 1. By examining IR spectra, it was deduced that ab- sorption bands at 3327.87 cm-1 in the first spectrum, 3349.88 cm-1 in the second spectrum and 3197.23 cm-1 in the third one represent OH valent vibration bands. C- H valent vibration bands of CH3, CH2 and CH groups are observed at 2922.29-2853.09 cm-1 in the first spec- trum, 2920.31-2851.84 cm-1 in the second spectrum and at 2916.63-2849.55 cm-1 in the third spectrum.
  • 5. Norwegian Journal of development of the International Science No 27/2019 5 Figure 1. IR spectra of the synthesized salts: a) salt 1; b) salt 2; c) salt 3 C-H deformational vibrations bands exist at 1459.23-1375.59 cm-1 , 1460.89-1378.84 cm-1 , 1462.47-1379.02 cm-1 , while C-N valent vibration bands are at 1259.26 cm-1 , 1284.93 cm-1 and 1285.88 cm-1 , respectively in the first, second and third spectra. C-O valent vibrations band of C-OH group can be de- fined at 1052.22 cm-1 in Salt 1 spectrum, 1047.67 cm-1 in Salt 2 and 1088.02 cm-1 in Salt 3 spectra. (CH2)x “pendulum”vibrations bands exist at 720.89 cm-1 in the first spectrum, 722.57 cm-1 in the second spectrum and 723.91 cm-1 in the third spectrum. Surface tension data of Salts 1, 2 and 3 were de- termined at temperatures 25, 24 and 26o C, respectively.  versus concentration (c) plots of the components are given in Figure 2. Figure 2. Surface tension at the water-air border versus concentration plots of the salts 0 20 40 60 80 0 0,0005 0,001 0,0015 0,002 0,0025 ,mN/m c, mol/l Salt 1 Salt 2 Salt 3
  • 6. 6 Norwegian Journal of development of the International Science No 27/2019 Bu using these plots of the salts, characteristic pa- rameters of the surface activity can be determined. Crit- ical micelle concentrations (CMC) of the salts were found out as 5.28*10-5 , 1.78*10-5 and 3.58*10-5 mol/l respectively. Additionally, CMC, surface pressure (πCMC), C20 (the concentration for reduction of  by 20 mN/m), adsorption efficiency (𝑝𝐶20 = −𝑙𝑜𝑔𝐶20) as well as CMC/C20 values of the all salts were determined according to [3] and given in Table 1. Maximum surface excess concentration-Г 𝑚𝑎𝑥 val- ues were calculated from the following equation: Г 𝑚𝑎𝑥 = − 1 𝑛 ∗ 𝑅 ∗ 𝑇 ∗ lim 𝑐→𝑐 𝐶𝑀𝐶 𝑑  𝑑 𝑙𝑛𝑐 where R is universal gas constant (R=8.3145 C/mol*K) and T is absolute temperature. The value of n was taken as 2 because 2 ions are formed by dissoci- ation of the salts. The minimum value of the area for one surfactant molecule of the salts at the water-air border (Amin) were determined by the given equation 𝐴 𝑚𝑖𝑛 = 1016 𝑁𝐴 × Г 𝑚𝑎𝑥 and tabulated in Table 1. Table 1 Surface activity parameters of the synthesized surface-active salts Surfactant CMC×105 (mol/L) CMC (mN/m) πCMC (mN/m) C20×105 (mol/L) CMC/ C20 pC20 Γmax×1010 (mol/cm2 ) Amin×102 (nm2 ) Salt 1 5.28 32.16 39.84 0.57 9.26 5.24 2.97 55.9 Salt 2 1.78 31.37 40.63 1.07 1.66 4.97 5.41 30.71 Salt 3 3.58 28.23 43.77 0.99 3.62 5.01 2.48 66.85 Specific electrical conductivity dependence on concentration was studied for the first salt-at 24.8o C, for the second salt-at 26.4o C and for the third salt-at 26.2o C. Isotherms of the specific electrical conductivity were plotted and given in Figure 3: Figure 3. Specific electrical conductivity versus concentration plots of the obtained salts Slopes of the straight line before (S1) and after (S2) CMC value of each salt were determined. Such thermo- dynamic properties as Gibbs free energy of micelliza- tion (ΔGmic) and Gibbs free energy of adsorption (ΔGad) values were calculated according to the following equa- tions: 𝛥𝐺 𝑚𝑖𝑐 = (2 − α) × 𝑅 × 𝑇 × ln(𝐶𝑀𝐶) 𝛥𝐺 𝑎𝑑 = (2 − α) × 𝑅 × 𝑇 × ln(𝐶𝑀𝐶) − 0.6023 × 𝜋 𝐶𝑀𝐶 × 𝐴 𝐶𝑀𝐶 where 𝐴 𝐶𝑀𝐶 is surface area of the one surfactant molecule at the interface in terms of Å2 . Table 2 Specific electrical conductivity parameters and thermodynamic parameters of micellization and adsorption of the obtained salts Surfactant α Β ΔGmic, kJ/mol ΔGad, kJ/mol Salt 1 0.29 0.71 -41.73 -43.07 Salt 2 0.03 0.97 -53.38 -54.13 Salt 3 0.02 0.98 -46.82 -48.58 As is seen, the ΔGad values are more negative than the ΔGmic values which points out to preference of the adsorption of the surfactants rather than the micelle for- mation. In order to identify petrocollecting property of the surface-active salts, unthinned reagents, 5% wt. aque- ous and ethanolic solutions of the salts were separately added to the water with thin petroleum layer. Thin layer (~0.17 mm) of Pirallahi (oil field near Baku, Azerbai- jan) petroleum was formed on the surface of 40 ml dis- tilled, tap and sea (the Caspian) water in Petri dishes. For each salt, maximum duration of the petrocollecting action and maximum petrocollecting coefficient-K at room temperature were determined and given in Table 3. The value of “K” is derived as the ratio of the area of the surface of initial petroleum film and the area of the 0 5 10 15 20 25 30 35 40 45 0 0,0005 0,001 0,0015 0,002 0,0025 κ,µS/sm c, mol/l Salt 1 Salt 2 Salt 3
  • 7. Norwegian Journal of development of the International Science No 27/2019 7 surface of the petroleum spot formed under the action of the salts. Table 3 Maximum duration of petrocollecting action and maximum petrocollecting coefficients of the synthesized salts Surfactant State of surfactant Duration, hours Maximum petrocollecting coefficient Distilled water Tap water Sea water Salt 1 Unthinned reagent 191 39.06 36.80 36.80 5% wt. aqueous solution 33.97 33.97 33.97 5% wt. ethanolic solution 31.54 31.54 29.44 Salt 2 Unthinned reagent 191 33.97 33.97 31.54 5% wt. aqueous solution 33.97 31.54 31.54 5% wt. ethanolic solution 33.97 31.54 30.45 Salt 3 Unthinned reagent 167 22.08 11.04 11.04 5% wt. aqueous solution 12.62 9.81 9.81 5% wt. ethanolic solution 14.72 9.81 9.81 As becomes evident from the obtained data, Salt 1 is more effective than the other two salts. In the sea and fresh waters, Kmax for Salt 1 is 36.8, whereas for the other two salts this index is lower. Aqueous solution of Salt 1 is more effective than its ethanolic solution. REFERENCES: 1. H.H.Humbatov, R.A.Dashdiyev, Z.H.Asadov et.al. Chemical Reagents and Petroleum Production, Baku:Elm, 2001,448 p. 2. Asadov Z.H. Azerbaijan oil industry. 2009, №2, p. 60-65. 3. Asadov Z., Ahmadova G., Rahimov R. Et al. Synthesis and Properties of Quaternary Ammonium Surfactants Based on Alkylamine, Propylene Oxide and 2-Chloroethanol, Journal of Surfactants and Detergents. 2018,21. p.247-254. 4. Asadov Z., Zarbaliyeva I., Zargarova S. Propoxylation of Aliphatic Amines by Propylene Oxide, Journal of Chemical Problems, 2017,1. p.44-50. 5. S.H.Zargarova, I.A.Zarbaliyeva, R.A.Rahimov, Z.H.Asadov. Synthesis and Study of Surface-Active Salts Based on Propoxy Derivatives of Dodecylamine and Monocarboxylic Aliphatic Acids. Proceedings of International Scientific-Practical Conference on Petroleum and Gas Industry, Almetyevsk (Russia), 2018, p.587-589. 6. M.J.Rosen. Surfactants and Interfacial Phenomena, 3rd Edn.New York: John Wiley and Sons, Inc-2004,444p. ACETYLTHIOUREA LEACHING GOLD FROM TAILS OF FLOTATION DEPOSIT DZHIKIKRUT Kholov Kh. Assistant of the name of V.I.Nikitin Institute of Chemistry, Academy of Sciences of the Republic Tajikistan Samikhov Sh. Doctor of Technical Sciences, The Leading sciences of the name of V.I.Nikitin Institute of Chemistry, Academy of Sciences of the Republic Tajikistan АЦЕТИЛТИОМОЧЕВИННОЕ ВЫЩЕЛАЧИВАНИЕ ЗОЛОТА ИЗ ХВОСТОВ ФЛОТАЦИИ МЕСТОРОЖДЕНИЯ ДЖИЖИКРУТ Холов Х.И. аспирант Института химии им. В.И. Никитина Академии наук Республики Таджикистан Самихов Ш.Р. доктор технических наук, главный научный сотрудник Института химии им. В.И. Никитина Академии наук Республики Таджикистан Abstract The presented results of the study on gold leaching proved that after pretreatment of tailings, acetylthiourea satisfactorily leaches gold from them. Аннотация Представленные результаты исследования по выщелачиванию золота доказывают, что после предва- рительной обработки хвостов ацетилтиомочевина удовлетворительно выщелачивает из них золото.
  • 8. 8 Norwegian Journal of development of the International Science No 27/2019 Keywords: acetylthiourea, leaching, trivalent ferrous sulfate, sulfuric acid, gold-antimony-mercury ore, gold- containing solution. Ключевые слова: ацетилтиомочевина, выщелачивание, трёхвалентный сульфат железа, серная кис- лота, золото-сурьмяно-ртутная руда, золотосодержащий раствор. Для выщелачивания золота из золотосодержа- щих руд широко используется цианирование. Во- преки преимуществу перед другими растворите- лями, высокая токсичность цианидов вынуждает искать альтернативные растворители золота, удо- влетворяющие ужесточенным экологическим тре- бованиям. Целая группа нецианистых растворите- лей – тиомочевина (тиокарбамид), гидросульфиды, хлор, тиосульфаты натрия и аммония, бром и соли гуминовых кислот изучены в Иргиредмет [1, с.415]. Тиокарбамидное выщелачивание, произведен- ное тем или иным способом, – перспективный гид- рометаллургический процесс извлечения золота [2, с.141]. Для проведения этого процесса необходимо применять эффективный окислитель, способный переводить металлическое золото в ионное состоя- ние и поддерживать низкие значения pН с целью предохранения от разложения золотосодержащего комплекса. Это достигается путем введения в про- цесс серной кислоты и сульфата трёхвалентного железа. Для снижения расхода тиокарбамида предва- рительно окисляют сульфиды железа, сурьмы, меди в кислой среде гидроксидом железа [3, с.182]. Из тиокарбамидных растворов золото осаждают це- ментацией свинцом, цинком, алюминием, сорбцией на активных углях, щелочами, электролизом. В промышленном масштабе тиомочевина при- меняется лишь на предприятиях с очень богатым концентратом, что оправдывает затраты на реагент. В России в итоге испытаний на опытных установ- ках выявлены неисправность способа: длитель- ность операции закисления, высокий расход кис- лоты, обогащение продуктивных растворов эле- ментами примесями и др. [3, с.189]. Эксплуатационные затраты при тиокарбамид- ном выщелачивании в целом примерно на 25 % меньше, чем для цианирования за счет существенно (более чем в три раза) меньших затрат на обезвре- живание промышленных стоков. Нами в лаборатор- ных условиях проведены исследования по ацетил- тиомочевинному выщелачиванию золота из хво- стов флотации нижнего горизонта месторождения Джижикрут [5, с.534]. Исследования в области выщелачивания кон- центрата проводились в стеклянных стаканах емко- стью 500 мл, использовавшейся стеклянной гидро- мешалки с двумя лопастями. Навеска концентрата, заваливавшегося в склянку, прибавлявшийся рас- твор ацетилтиомочевины и серная кислота, давав- ший окислитель трёхвалентного сульфата железа и производилось размешивание в течение определён- ного промежутка времени. После 2,4,6,8 часов по- сле начала исследование мешалку останавливали, и производился отбор аликвоты для определения рН и концентрации золота. В растворах золото опреде- лялось методом атомно-абсорбционной спектро- скопии. Испытание проводилась в 1 %-ном рас- творе ацетилтиомочевинны при 1,38 % серной кис- лоты и 0,5 % трёхвалентного сульфата железа. Дли- тельность время опытов 8 часов, рН среды - 6,0. Золото в раствор, в данных условиях, переходило в незначительных количествах (таблица 1). Оче- видно из таблицы 1 и рисунка 1, за 8 часов в раствор выщелачивается Au – 20,8%. Ради улучшения процесса ацетилтиомочевин- ного выщелачивания пробы хвостов флотации под- вергались обжигу при температурах 200 – 600 °С в продление 2 часов. В абразии и при обжигании про- исходит вскрытие упорных золото - сульфидных концентратов, в то же время минералы пирит и ар- сенопирит окисляются, по этой причине происхо- дит вскрытие содержащегося в них золота. Таблица 1 Извлечение золота благодаря ацетилтиомочевинному выщелачиванию хвостов флотации нижнего горизонта Джижикрутского месторождения Время, ч Правило опыта Концентра- ция Au в растворе, мг/л Извлечение Au, %руда, г вода, мл CH3CONH CSNH2, г H2SO4 (конц.), мл. Fe2(SO4)3, г pН Нач. 100 200 2 1,5 1,5 2 1,0 5,8 0,165 19,4 4 6,1 0,174 20,5 6 5,8 0,175 20,6 8 5,8 0,177 20,8
  • 9. Norwegian Journal of development of the International Science No 27/2019 9 Рис.1. Выщелачивание золота при температурах 200 0 С Окисление пирита начинается возле темпера- туры 450 – 500 °С. Процесс протекает с образова- нием как промежуточного продукта пирротина. FeS2 + O2 = FeS + SO2, окисляется до магнетита 3FeS + 5O2 = Fe3O4 + 3SO2 и через некоторое время до гематита 2Fe3O4 + 1 /2O2 = 3Fe2O3. В таблицах 2,3 и рисунках 2,3 показаны испытанные результаты. Очевидно из таблицы и рисунка, за исключе- нием кислотной обработки хвостов, обожженных благодаря температуре обжига 200 0 С в раствор пе- реходило 19,5 % золота, а около 400 °C с последу- ющим выщелачиваем ацетилтиомочевинной в рас- твор переходит всего лишь 21,6 % золота. Увеличе- ние температуры обжига до 600 °С способствует тому, что извлечение золота повышается до 45,2 %. Только после обжига при температуре 600 °С вследствие рН = 1,2 в раствор переходило 83,3 % с дальнейшей кислотной обработкой спустя 8 часов извлечение золота в раствор из хвостов составило 86,1 %. Таблица 2 Извлечение золота благодаря ацетилтиомочевинному выщелачиванию хвостов флотации нижнего горизонта Джижикрутского месторождения Время, ч Правило опыта Концен- трация Au в рас- творе,мг/л Извлече- ние Au,% руда, г вода, мл CH3CONHCSNH2, г H2SO4 (конц.), мл. Fe2(SO4)3, г pН нач. 100 200 2 1 1 2 5,8 0,165 19,4 4 6,1 0,174 20,5 6 5,8 0,175 20,6 8 5,8 0,177 20,8 Хвосты флотации после обжига при 200 0 С 2 5,3 0,144 16,9 4 5,3 0,152 17,9 6 5,8 0,168 19,8 8 5,8 0,166 19,5 Хвосты флотации после обжига при 400 0 С 2 5,6 0,162 19,0 4 5,9 0,173 20,3 6 6,2 0,181 21,3 8 6,0 0,184 21,6 Хвосты флотации после обжига при 600 0 С 2 6,2 0,338 39,8 4 6,4 0,379 44,6 6 6,2 0,381 44,8 8 6,8 0,384 45,2
  • 10. 10 Norwegian Journal of development of the International Science No 27/2019 Рис.2. Зависимость извлечения золота от времени при температурах 200 до 600 0 С Таблица 3 Извлечение золота благодаря ацетилтиомочевинному выщелачиванию хвостов флотации позже об- жига при температуре 600 0 С Время, ч Правило опыта Концен- трация Au в растворе, мг/л Извлече- ние Au, % руда, г вода, мл CH3CONHCSNH2, г H2SO4 (конц.), мл. Fe2(SO4)3, г pН нач. 100 200 2 20 1 2 1,6 0,631 74,2 4 1,4 0,663 78,0 6 1,4 0,700 82,3 8 1,2 0,708 83,3 Хвосты флотации после обжига при 600 0 С + обработка серной кислотой 2 2,4 0,648 76,2 4 2,8 0,685 80,6 6 2,6 0,730 85,9 8 2,6 0,732 86,1 В ходе исследования ацетилтиомочевинного выщелачивания золота из руд выявлены следую- щие его преимущества как растворителя по сравне- нию с цианированием: низкая токсичность, исклю- чение из схемы необходимости обезвреживания стоков, отвалов и т.д.; высокая скорость растворе- ния металлов, меньшее воздействие на компо- ненты-примеси, слагающие руду; меньший расход реагента на единицу массы руды; более полное из- влечение золота в цикле выщелачивания, особенно при наличии в рудах его сульфидных форм; воз- можность осуществления комбинации отдельных стадий выщелачивания, направленных на улучше- ние технологических показателей (предваритель- ная кислотная обработка, окисление сульфидов или совмещение этих двух процессов); простая схема регенерации растворителя путем очистки от приме- сей (известкование), позволяющая осуществить бессточную гидрометаллургическую технологию.
  • 11. Norwegian Journal of development of the International Science No 27/2019 11 Рис.3. Зависимость извлечения золота из хвостов флотации до и после обжига при температурах 600 0 С и с обработке серной кислотой Следовательно, использование ацетилтиомо- чевины с целью выщелачивания золота из руд и хвостов флотации рентабельно. Помимо того, с применением ацетилтиомочевины извлечение зо- лота во много раз выше, чем при цианировании. СПИСОК ЛИТЕРАТУРЫ: 1. Лодейщиков В.В. Технология извлечения золота и серебра из упорных руд. В 2-х т. – Иркутск: ОАО «Иргиредмет», 1999, 786 с. 2. Захаров Б.А., Меретуков М.А. Золото: упорные руды. - М.: Руда и Металлы, 2013, 450 с. 3. Самихов Ш.Р., Зинченко З.А., Бобомуро- дов О.М. Изучение условий и разработка техноло- гии тиомочевинного выщелачивания золота и сере- бра из руды месторождения Чоре. – Доклады АН. - Душанбе, 2013 -т. 56, № 4 с. 181-184. 4. Лодейщиков В.В., Панченко А.Ф. Основы технологии извлечения золота и сурьмы из ком- плексных руд. – Интенсификация процессов обога- щения минерального сырья. – М.: Наука, 1981, с. 189-193. 5. Самихов Ш.Р., Холов Х.И., Зинченко З. А. Технология обогащения руд нижних горизонтов Джижикрутского месторождения. – Доклады АН РТ – 2017. Том 60. - №10 с. 533-538. UDC 541.64:544.032:577.12 EFFECT OF PLANT ENVIRONMENT ON DECOMPOSITION OF BIODEGRADABLE MATERIALS BASED ON POLY-3-HYDROXYBUTYRATE AND POLYLACTIDE Shibryaeva L. D. Sc., Prof., Leading researcher N. M. Emanuel Institute of Biochemical Physics, Russian Academy Sciences Federal Scientific Agroengineering Center VIM Tertyshnaya Yu. Ph.D., Senior Researcher N. M. Emanuel Institute of Biochemical Physics, Russian Academy Sciences Federal Scientific Agroengineering Center VIM Solovova Yu. Ph. D., Junior researcher N. M. Emanuel Institute of Biochemical Physics, Russian Academy Sciences Levina N. Senior researcher Federal Scientific Agroengineering Center VIM Zhalnin E. D.Eng, Prof., Head of Laboratory Federal Scientific Agroengineering Center VIM
  • 12. 12 Norwegian Journal of development of the International Science No 27/2019 Abstract Samples of nonwoven material from biodegradable polymers poly-3-hydroxybutyrate and polylactide used as carriers of wheat seeds, accelerate their germination compared to control. The nonwoven fabric is prepared by electroforming the fibers in organic solvents. Paper filters are used as a control. The influence of germinated seeds on the thermal parameters of melting and physical and mechanical properties of biodegradable polymer carriers is shown. It is established that there is a relationship between the destruction of the polymer material and the rate of germination of seeds, as well as the development of the root system of plants. It is shown that the destruction of polymers proceeds through several mechanisms, which depend on the stage of seed germination. At the initial stage, the mechanism of hydrolytic degradation and enzymatic catalysis of polymers is considered. The process of polymer destruction by mechanical destruction under the influence of growing roots is discussed at the stage of root system development. The development of the root system leads to the appearance of microcracks, their fusion with the formation of holes in the polymer material. The kinetics and mechanism of destruction of the seed carrier polymer and the growth rate of the root system depend on the nature and structure of the polymer. Nature determines the direction of crack germination in the polymer carrier for polylactide - along its surface, for poly-z- hydroxybutyrate in volume. Keywords: wheat seeds, biodegradable polymers, nonwoven materials, poly-3-hydroxybutyrate, polylactide, destruction. Introduction The most important task of the agro-industrial complex of any contry is the introduction of innovative technologies aimed at increasing the yield of agricultural crops and the creation of environmentally friendly products. These technologies are based on non- traditional methods of cultivation and storage of agricultural products. Among them are the technologies of mulching soil, pelleting seeds of onions, carrots, tomatoes and other vegetables, based on the use of film materials from biodegradable compositions based on natural and synthetic polymers [1-4]. Recently, the technology of planting seeds in the soil on a polymer tape has been developed for grain crops in Russia [5,6]. The use of the tape involves the provision of environmentally friendly conditions for germination of seeds of grain crops, their protection from the effects of pathogenic systems, the creation of a microclimate favorable for seed germination and plant development. This technology is extremely important for seed farms. It is supposed that the tapes filled with seeds together with mineral fertilizers can create conditions for production of elite grades of grain crops. The main requirement for the materials used for the manufacture of tapes-carriers of seeds, is their ability to provide conditions for the life of crops. First of all, such materials, in contact with germinating seeds and plants, should not only not violate the mechanism of their development, but also stimulate these processes. The materials must be predisposed to degrade under the action of biological fluids, oxygen, UV- radiation with a high speed with the formation of environmentally friendly products, not contaminating the soil. At the same time, it must have mechanical parameters that can ensure the planting of seeds in the carrier tape into the soil with the help of agricultural machinery. Today there is a problem of creation of a material for tapes – carriers of seeds capable to solve objectives. The most suitable materials that can meet the requirements are biopolymers based on oxy-derived fatty acids, the so - called polyhydroxyalkanoates, the main advantages of which are their high physical and mechanical properties and environmental friendliness [7]. Poly-3-hydroxybutyrate (PHB) and polylactide (PLA) were used for agricultural purposes in [8-10]. Properties of these polymers provide their wide application in agricultural and food industry, medicine and biology [11-16]. They undergo biodegradation in enzymatic catalysis under the action of bacteria and fungi [12]. It is important for the metabolism of plant cells that the stresses arising in polymer chains, causing the decay of bonds, initiate radical chain processes of oxidation of macromolecules [13]. The decomposition products of these biodegradable polymers are carbon dioxide and water. However, to date, there are no studies of the processes of biodegradation of polymers under the influence of the environment which created by germinating seeds and developing plants. The aim of the work was to establish patterns of biodegradation of polymer materials based on PHB and PLA under the influence of germinating wheat seeds. Experimental part Poly-3-hydroxybutyrate (PHB) of German firm "Biomer" with molecular weight Mw=2,5×105 g/mol in the form of fine powder, d = 1,248 g/cm3; polylactide (PLA) of brand 4032D manufactured by "Nature Works" (USA) with Mw=1,7×105 g/mol in the form of granules, with d =1,27 g/cm3 ; mixtures of PHB with synthetic nitrile rubber (SNR) were used in the work. SNR of Russian production with 28 wt.% of nitrile groups, with the Mooney viscosity at 100o C - 45 c. u., PHB-SNR mixtures contained 30 wt.% rubber's were used. Samples in the form of extruded films and nonwoven material were investigated. Films with thickness of 80 - 120 mcm was obtained by pressing PLA at 195-200, PHB at 150-175о С, with subsequent slow cooling. The nonwoven material was prepared from nanofibers obtained by electroforming by exposure to an electric voltage of 10-60 kV to an electrically charged jet of 6% solution of each of the polymers in chloroform or in a mixture of chloroform with dichloroethane in a ratio of 80:20 wt.% arising from the capillary nozzle [17,18]. We studied the germination, germination of seeds, growth and development of seedlings of spring wheat varieties "Athena" (Triticum aestivum) harvest in 2015 (Krasnodar region) in the laboratory. For seed
  • 13. Norwegian Journal of development of the International Science No 27/2019 13 germination, they were placed in Petri dishes of 50 seeds in accordance with GOST 12038-84 [19] on moistened pads made of paper filters or polymer material. Samples were filled with distilled water so that moisture covered the seeds. Germinating seeds were kept in a thermostat at a temperature of 20±1 ° C, maintaining a constant level of humidity. As a reference to monitor the germination of seeds and development of plants on the polymeric samples was used a substrate of disinfected paper filters brand Blue ribbon FM without impurities on the other 2642- 001-68085491-2011. After 1,2,3 days, the number of sprouted seeds was determined as a percentage in each batch of samples taken for analysis (at least 5 samples). Seed germination energy was defined as the percentage of normally sprouted seeds in the first three days. Germination-on the seventh day. During 14 days the dynamics of growth of wheat roots and seedlings was analyzed. Experimental data were processed using dispersion and correlation analysis according to the programs "AGROS-2.02". The accuracy of determining the germination parameters is not less than 1.5%. The thermophysical characteristics of polymer materials were determined using a differential scanning calorimeter of the company ("Netzsch", Germany, model DSC-204 F1) at a heating rate of 10 deg/min in the temperature range of 30-200 ° C in argon current. A portion of the sample was varied in the range of 2÷8 mg using DSC received values of the heats and melting points of PHB and PLA. To accurately determine the parameters, corrections were introduced into the recorded values for the parameters of the melting peak indium (with the temperature and heat of melting of Tm=156.7°C and Hm=28.58 J/g). The heat of fusion was determined by the crystallinity of the PHB and PLA ratio =(ΔHm / ΔH*m) × 100%, where ΔHm - the heat absorbed during the melting of the sample per unit mass of pure polymer, ∆H*m - the specific heat of fusion of crystals of PHB and PLA is 90 [20] and 106 J/g [21], respectively. The accuracy of the melting temperature of the Tm is±1 ° C. Standard deviations of experimental areas of melting peaks of different samples (at least 10 samples) were within 10%. The surfaces of the polymer samples, the structure and thickness of the fibers of the nonwoven material were investigated using an optical microscope Axio with a thermal imager Z2m, Carl Zeiss with software; with 50×, 200×, 500× magnification in both transmitted and reflected light. Physico-mechanical parameters, including tensile stress (F), relative elongation (ε), breaking length (L) of PHB and PLA samples were determined on a tensile testing machine RM-3-1 according to GOST 25.061065-72. The speed of movement of the lower clamp is set 45±5 mm/min. Samples of seeds grown on substrates during 9 and 14 days were dried, cleaned from the root system of plants and cut in the form of blades. The parameters were calculated by load – elongation curves. To obtain each value, 2 batches containing at least ten samples were used. Standard deviations of experimental parameters were within ± 20%. The parameters of water absorption of a solution of amylase, extracted from the seeds and roots of wheat, nonwoven material and polymeric films of native seeds was determined according to GOST 4650-80 [22]. The tests were carried out on square-shaped samples of ~30×30 mm in size by at least 3 for each material. Before determining the parameters, the samples were dried at (50±2)°C for (24±1) hours, then cooled in the desiccator above the desiccant at (23±2) ° C. After cooling, the samples were weighed for 5 minutes. After that, the samples were placed in vessels with distilled water and amylase extract. On 1 cm2 of the sample surface there was at least 10 cm3 of liquid. The liquid with the sample placed in it was stirred by rotating the vessel at least once a day. When determining the maximum degree of swelling in the water (to equilibrium), the equilibrium was considered achieved if the difference between the mass of the sample determined with an interval of 24 hours did not exceed 0.1 %. After that, the samples were removed from the vessels and placed on a clean filter and removed moisture from the surface. Then weighed on electronic scales. The degree of water absorption and absorption of amylase solution was calculated by the formula: α = (m -mo)/ mo . 100%, where mo – the initial mass of the sample, m – the mass of the sample after saturation with water or a solution of amylase during time . IR spectroscopy and optical microscopy were used to control the filling of amylase films. IR spectra were obtained using a Fourier transform spectrometer of the company Perkin-Elmer. Results and discussion Important indicators of the possibility of using biodegradable materials for the technology of growing wheat as substrate – carriers of seeds is the ability of the material to destruct in contact with germinating seeds and at the same time affect the rate of germination of seeds and the development of various organs of the plant. In order to establish the feasibility of using of materials, based on poly-3-hydroxybutyrate and polylactid, for carriers of seeds, were carried out laboratory studies of dynamics of germination of wheat seeds on their surface in an aqueous medium (in Petri dishes). We used samples of extruded films and nonwoven material made of polymers PHB, PLA, and mixtures of PHB-SNR structures. In the course of the work the regularities of changes in thermophysical and physico- mechanical parameters of the above samples under the influence of germinating seeds and developing root system with seedlings were studied. With the aim of establishing a relationship between the kinetics of destruction of the polymer and the dynamics of plant development parameters of germination, energy of germination and biometric parameters of wheat germ that grew on the samples of polymer materials were compared with similar parameters obtained for seeds
  • 14. 14 Norwegian Journal of development of the International Science No 27/2019 germinated on paper filters, performing the role of control samples. The results are presented in table. 1. Table. 1. Indicators of germination and biometric parameters of wheat seed seedlings of the "Athena" variety (Triticum aestivum). Comparison of the parameters of the germination and biometric parameters of seedlings of wheat seeds (table. 1) demonstrates noticeable differences in the indicators of seeds sprouted on polymer carriers from the control samples. When comparing samples of different polymeric carriers, differences in the germination rates of seeds germinating on them were found. Moreover, these differences depend on the chemical composition and structure of the substrate. On substrates of nonwovens seed germination and development of the root system on them are significantly accelerated compared to the control substrates of paper filters, while the pressed films seed germination slows and plant growth is inhibited (table. 1). At the study of the dynamics of seed germination on carriers of nonwovens was found to increase the effect of the impact on the seeds in the transition from the stage of ontogenesis with the formation of the root to the stage of growth and development of the root system and seedlings (table. 2). If at the stage of ontogenesis there is a tendency to increase the quantitative parameters (germination and energy of seed germination) in comparison with the control, then at the stage of growth there is a significant increase in biometric indicators (table. 2). Table 2. The dynamics of germination of wheat seeds on different carriers Figure 1 shows a significant increase of differences between the parameters of seed seedlings, root system and wheat germ grown on the surface of the paper filter and of nonwoven material PHB with increased time of germination of seeds. As can be seen, the rate of development of wheat on a biodegradable polymer substrate is accelerating, which can be explained by the factor of initiation of growth processes on the part of the polymer. a b c d e f Fig. 1. Photos of samples of wheat seeds which sprouted in Petri dishes on the surfaces of substrates – carriers of seeds from paper filter (a, с, e) and nonwoven material from PHB (b,d,f) in the aqueous medium for 2 (a,b), 4 (с,d) and 7 (e,f) days
  • 15. Norwegian Journal of development of the International Science No 27/2019 15 The study of changes in polymer substrates – carriers in the process of germination of seeds and seedlings in the dynamics of the latter showed that developing plants are not indifferent to the polymer substrates and have a significant impact on the structural, physical and mechanical parameters of the latter. The germination of seeds and the development of seedlings on a sample of polymer material lead to its destruction, as evidenced by the decrease in mass. The results of the study of reducing the mass of samples in the process of destruction as a result of contact with germinating seeds are presented in table 3. Table. 3. The mass of samples of initial films and after germination of seeds in them As can be seen from table 3, the samples of nonwoven material from PHB and PLA, being in direct contact with the plants for 9 days decreased in weight by 1.4 and 2.2 times respectively. It is important to note that the samples has been dried and prepared for out weighing to obtain these results. It was taken into account that after the experiment some part of the plant roots was directly in the material, however, even with its mass significantly decreased compared to the mass of the original sample (table. 3). The development of the root system on polymer carriers causes changes in their physical and mechanical properties. On the tensile testing machine were tested samples of nonwoven material PHB and PLA, the original and after the experiment, in the continuation of which the material was in direct contact with the plant. The analysis of the obtained data showed that after germination of seeds in PHB the values of relative elongation, maximum load and breaking length are significantly reduced, in polylactide with a significant drop in the index of relative elongation, the maximum load and breaking length are increased by ~ 2.5-3 and 6 times, respectively (table. 4). I.e. is detected the dependence of the nature of the impact of growing roots on the polymeric carriers from their chemical structure. Table. 4. Physical and mechanical characteristics of seed substrates of nonwoven PGB, PLA initial and after germination of wheat seeds in them. Figure 2 shows photos of destructive samples of nonwovens PHB and PLA exposed to the root system and seedlings during wheat growth for more than 14 days. Figure shows a different picture of the destruction of polymers. Based on the picture of destruction of PHB and PLA, shown in Fig. 2 and data in table. 4, it can be assumed that the observed difference in the change in mechanical parameters of PLA and PHB samples under the action of developing plants is due to different mechanisms of biodegradation of these polymers. It is possible that a significant increase in the maximum load and breaking length in the PLA is due to the influence of the reinforcing layer that strengthens the matrix, which arose from the undeleted root residues due to the development of the root system along the surface of the carrier (Fig. 2). At the same time, the roots of PHB germination are carried out in the depth of the material, creating a “hole” in the polymer matrix (Fig.2). Fig. 2. Photographs of the samples of substrates of seeds from nonwoven material PHB (a) and PLA (b) with germinated in them root systems of wheat. Change of thermophysical parameters of samples of nonwoven material under the influence of germinated seeds was investigated by DSC method. The melting thermograms of crystallites were compared for the initial films – seed carriers before their planting and after germination of plants and substrates exposed to the growing root system. Fig. 3 presents an example of endothermic melting peaks for nonwoven PHB materials and the PLA before and after germination of seeds in them.
  • 16. 16 Norwegian Journal of development of the International Science No 27/2019 Fig.3. Endotherms of melting of samples of nonwovens PHB (1,2) and PLA (3,4,5), before (1,3) and after (2,4,5) germination of seeds in them within 9 (2,4) and 14 (5) days. Endotherms characterizing the melting of crystallites of the initial carriers of PHB and PLA have one peak in the temperature range 150-190o C with a maximum temperature (Tmax) equal to 172.8°C in PHB and 166°C in PLA. The nature of the change in the shape of the peaks in the samples after germinate the seeds were depends on the nature and structure of the polymer material and the time of seed germination (Fig. 3). The analysis of melting endotherms was carried out for 9 and 14 days of seed germination. The peak of melting of PHB is shifted to the low-temperature region by several degrees and a low-melting shoulder appears after 9 days (Fig. 3). Changes in the shape of PLA melting peaks depend on the time of root germination to a greater extent than that of PHB. For example, after 9 days of seed germination, there is a shift in the melting peak Tmax in the high-temperature region with the appearance of a low-melting shoulder nearby with Tmax of the initial sample (Fig. 3). After 14 days, the entire melting peak shifts to the low-melting region (Fig. 3). The change in the forms of melting peaks of PHB and PLA is accompanied by a drop in the melting heat, hence the degree of crystallinity (table. 5). The shift in melting temperatures and the decrease in the degree of crystallinity indicate the destruction of crystal structures. Table. 5. Thermophysical parameters of polymer samples of the substrates - carriers of the seed from nonwoven material From the difference of the magnitudes of the fall of the heat of fusion of the crystallites in samples of non-woven materials PHB, PLA, prepared from solutions in chloroform and mixtures of chloroform- dichloroethane (table. 5), the influence of the substrate structure on the seed germination rate is clearly observed (table. 1,2). Thus, the degree of crystallinity in samples of PHB prepared from CHF and CHF with EDC after germination of seeds in them is reduced by 1.8 and 1.1 times, respectively, in the sample of PLA from CHF by 1.1 times, in the sample mixture of PHB+ SCN-by 3-3. 5 times (table. 5). The greatest drop in the degree of crystallinity of the substrate corresponds to the largest mass and length of roots and seedlings (table. 1) and the highest seed germination index (table. 2). To the question about the mechanism of degradation of polymeric substrates under the action of growth of seeds of wheat
  • 17. Norwegian Journal of development of the International Science No 27/2019 17 An important task, the solution of which depends on the use of the studied materials as seed carriers, is to establish the mechanism and kinetics of biodegradation of the carrier under the action of germinating seeds and developing plants. Based on the literature data on the physiology of plants, as well as from the above results obtained in our work, it can be argued that the biodegradation of the polymers, which occurring in contact with germinating seeds, is not described by a single mechanism. The latter can vary depending on the stage of plant growth and the parameters of the polymer-seed carrier. At the ontogenesis stage, the determining factor of germination of seeds, is the rate of grain swelling and water supply to the embryo [23,24]. Germination of seeds on the surface of the polymer carrier will inevitably depend on the ability of the carrier to provide the embryo with water, hence the process of swelling of the polymer in contact with the grain and the rate of diffusion of water through the polymer to its surface. At this stage, the beginning of the destruction of polymer substrates may be due to swelling and caused by hydrolysis of polymer macromolecules. Biodegradation of polyethers based on polylactide and polyhydroxybutyrate is mainly carried out by hydrolysis of ether bonds by reaction: -COO- + H2O —> -COOH + HO- On the other hand, it is known that in the course of biochemical processes developing in germinating wheat grains, enzymes are formed, the main of which is amylase. Amylase can be run from the seed through the aleuronic layer into an aqueous medium in contact with the polymer. In this case, at the stage of seed germination with the formation of the embryos and root system, in contact with the surface of the polymer carrier in an aqueous medium, the conditions for the reaction of enzymatic hydrolysis of the polymer. As is known for the reaction of the formation of intracellular enzymes that lead to the growth of roots and seedlings, requires a lot of energy. This energy can be obtained by the destruction of biodegradable polymers. Because the observed acceleration of seed germination on substrates of nonwoven materials PHB and PLA compared to the control samples, it is possible to hypothesize about the existence of the mutual influence of the speed of seed germination and the decomposition of the polymeric substrate and its nature. The essence of this effect is that the polymers in contact with the seeds in the aqueous medium, subjected to enzymatic hydrolysis under the action of amylase released from the seeds, are energy "food" for the development of biochemical processes of formation of enzymes that stimulate the germination of plant seeds. To test the above hypothesis, the kinetics of hydrolysis of polymer carriers in distilled water and aqueous amylase solution was studied. Amylase solutions were prepared by extraction of the enzyme from swollen seeds. Kinetic curves were obtained that characterize the swelling of polymer samples of pressed PHB film and nonwovens PHB and PLA and hydrolytic degradation under the action of water, as well as enzymatic decomposition in an aqueous solution of amylase. These curves are shown in Fig. 4. Fig.4. Kinetic curves of swelling of samples of nonwoven material PHB (1), PLA (2), extruded films PHB (3) in distilled water, sorption and hydrolytic degradation of nonwoven materials PHB (4) and PLA (5) in the water extract of amylase and the curve of swelling of wheat seeds in water (6).T=22o C. As can be seen from the figure within the selected time interval, the kinetic swelling curves of the studied samples have a typical form of the process with an accelerated initial stage and a stationary site. The kinetics of swelling of nonwoven material in water is described by the equation [22]: , (1) , (2) где k - the rate constant of swelling α -
  • 18. 18 Norwegian Journal of development of the International Science No 27/2019 αmax – maximum degree of swelling, From these curves it can be seen that the studied samples differ in the values of the swelling rates at the initial site and the maximum degrees of swelling max max of the pressed film PHB is significantly lower (40- max of the nonwoven material of PHB is greater (380%) than PLA (240%). The swelling rate constants (k) for the initial stages of water saturation (3 days) of polymer samples, were estimated by equations (1) and (2), were equal ~0.088, ~0.1136, ~0.1144 h-1 for PHB films, nonwovens PHB and PLA, respectively. For comparison, in Fig. 4 the kinetic curve of swelling of seeds in the aqueous medium (curve 6) to the stage of their germination is presented. This curve includes the stage of seed swelling, passing into the stage germination with the appearance of roots and seedlings for 3 days. The constant swelling rate (before the emergence of seedlings), estimated for seeds similar to polymer substrates, was ~0.12 h-1 , which is within the same range with the data obtained for polymer substrates of nonwoven materials. Since the water diffusion coefficient of nonwoven PHB material (density ρ = 0,12 - 0,21 g/cm3 DH2O = 4.0 10-10 cm2 /s ) is higher than from the extruded film PHB (DH2O is 3.6.10-11 cm2 /s [25,26]) may be to conclude that for a friable structural organization of the nonwoven material is characteristic not only a greater degree of swelling of seeds, but and it increase of rate of diffusion of water towards its embryo, this is determines the growth rate germination of seed in contact with nonwoven material. Kinetic curves presented for non-woven fibers of PHB and PLA after their stand in an aqueous extract of wheat seeds containing amylase (Fig. 4, curves 4.5), demonstrate a significant effect of the enzyme. (The appearance of amylase in the aqueous medium was recorded by changing the pH of the aqueous medium with swollen grain and its UV- spectrum). In place of hydrolytic destruction is enzymatic hydrolysis. It is important that these curves can distinguish the initial stage characteristic of the swelling process in water with increasing sample mass. After the first stage, there is a loss of polymer mass, indicating enzymatic hydrolysis (curves 4,5). A particularly high rate of mass loss is observed in the sample of PHB (curve 5), in PLA this rate is lower (curve 4). When comparing the kinetic curve of swelling of seeds in the aqueous medium (Fig. 4, curve 6) with a curve of the enzymatic hydrolysis of non-woven fibers (especially for PHB (Fig. 4, curve 4) reveals that the time corresponding to the beginning of the selection of the enzyme and the emergence of seedlings in the swelling of the seed (~3 days) corresponds to the beginning of the fall weight of the polymer on the curve of enzymatic hydrolysis. The penetration of water into the seed substrate material, leading to hydrolysis in water and enzymatic decomposition in the enzyme solution, initiates violations in its structure. This follows from the comparison of the thermophysical parameters of melting of the crystal structures of the studied samples of the original nonwoven materials PHB and PLA, with the treated aqueous medium and enzyme extract of seeds obtained by DSC. The melting endotherms of polymer samples, after swelling in water for 144 hours (previously dried at room temperature to a constant weight), show a shift of the melting peak by several degrees towards high temperatures, with the appearance of a low-melting shoulder (Fig. 5). This is due to the recrystallization of the polymer, which occurs under the influence of water molecules localized in the amorphous regions. From the melting endotherms of samples hydrolyzed in amylase, a significant destruction of the crystal structure of the polymer follows. This is evidenced by the shift of the maximum melting peak for PHB and PLA towards low temperatures ~to 10 degree (Fig. 5). At the same time, the melting heat reduction reaches 9% (table. 6). It is important to note that a significant decrease in the melting temperature, indicating the enrichment of the crystalline structures of low-melting fraction of crystallites characteristic of enzymatic hydrolysis. Fig.5. Endotherms of melting samples of nonwoven PHB material: initial (1) exposed to aqueous medium (2) and amylase extract with pH=11 (3).
  • 19. Norwegian Journal of development of the International Science No 27/2019 19 Table. 6. The thermophysical parameters of samples of nonwoven material PHB, treated with water and extract with amylase and enzymes It is known that the rate of hydrolysis is different for materials with different chemical and physical structures and depends on the presence of crystalline regions in the polymer, access to which is difficult. Hydrolysis can occur mainly on the surface of the polymer material, and in its volume. Perhaps the hydrolytic destruction of nonwoven PHB and PLA material in amylase affects their molecular structure in different ways. Usually for polylactide hydrolysis acceleration in the depth of the product occurs in the case of pH drop caused by acidic degradation products. However, in our case, the observed decrease in the rate of falling weight of PLA in the medium of wheat seed extract containing amylase, the process takes place in an alkaline medium at pH = 11. Saturation of polymer films with amylase was controlled by IR spectra. Visible decrease in the rate of PLA degradation, observed from the enzymatic hydrolysis curves (Fig.4, curves 4.5), can be explained by the surface process (erosion). A sharp drop in the mass of PHB indicates that the destruction process develops in the volume of the polymer. The fact of different localization of hydrolysis of PHB and PLA confirms the comparison of the pictures presented on microphotographs (Fig. 6), demonstrating the surface of the samples of nonwoven materials of PHB and PLA, obtained after filling with amylase from the extract and after the last destructive processes of enzymatic hydrolysis (Fig. 6). In the PLA sample, small cracks and small depressions are observed along the entire surface. In PHB-clearly expressed significant depressions and pits, locally distributed in separate zones on the surface of the polymer (Fig. 6). Fig.6. Microphotographs of samples of nonwoven material PHB (a, b) and PLA (c, d), initial (a, c) and sub- jected to enzymatic hydrolysis for 6 days under the action of an aqueous extract of amylase from germinating seeds (b, d). It should be noted such experimental results as: first, the quantitative relations between the rate constants of swelling of polymers and seeds in water (Fig. 4, curves 1,2,4,6); secondly, the ratio between the time of amylase release into the aqueous medium and the beginning of seed germination and the time corresponding to the process of enzymatic hydrolysis of the polymer substrate material (Fig.4 curves 4,6); third, the destruction of the crystal structures of the studied polymer samples under the action of enzymatic hydrolysis (Fig. 5); fourth, the data optical microscopy of the surface, reflecting the nature of the enzymatic hydrolysis of PHB and PLA in the seed extract (Fig. 6). Apparently, these results confirm the possibility of implementing the above hypothesis about the nature of the stimulating effect obtained from polymer carriers at the initial stage of seed germination as an effect caused by enzymatic hydrolysis of the polymer substrate. The possibility of the enzymatic hydrolysis of the carrier during the germination of seeds on it was evaluated by the effect on the nonwovens of PHB aqueous extract of enzymes isolated from sprouted roots. The extract was prepared from the mass of roots grown after 9 days of seed germination. The melting endotherms of PHB obtained after treatment with this extract for several days demonstrated the same
  • 20. 20 Norwegian Journal of development of the International Science No 27/2019 character of changes in the polymer melting parameters that was observed in the sample treated with amylase from seed extract. The differences were in a greater drop in heat and melting temperature - a greater shift of the peak to the low-temperature region (table. 6). Comparison of melting parameters of polymeric carriers of seeds on the example of samples of nonwoven PHB material exposed to seed germination before the stage of root formation, with samples exposed to enzymatic hydrolysis, indicates the presence of polymer destruction in both cases. However, the mechanisms of destruction are different. If the of seed carrier, under the action of the root system, there is mainly a significant drop in crystallinity, i.e. amorphization of the polymer (table. 5), that the sample, which subjected to hydrolysis, changes the structure of the crystalline regions without a significant drop in their volume. For example, samples of PHB with sprouted roots reduce the melting temperature of crystallites (Tmax) to ~4o C with a significant drop in the degree of crystallinity (from ~47 to 70%) (table 5). In the sample subjected to enzymatic hydrolysis, the decrease in Tmax reaches 8-10o C. At the same time, the degree of crystallinity varies by 9% (table. 6). Comparison of the curves of temperature dependences for the degree of transformation of crystalline structures into melt during melting of nonwoven material PHB demonstrates the differences in shape of curves in samples, subjected to enzymatic hydrolysis and in the samples after formations in them of the root system ( Fig. 7). Obviously, this is due to different laws of melting of PHB, due to different mechanisms of destruction of polymeric materials. Fig.7. Curves of the temperature dependence of the degree of conversion the crystallites PHB into the melt dur- ing melting of the nonwoven material PHB for initial sample (1), for sample after germination into it of the root system (2) for samples which were subjected to a water environment (3) and amylase (4) Apparently, the contribution into the destruction of the polymeric substrates - carriers of the enzymatic hydrolysis process, can be come to light at the stage of ontogenesis, at the stage of formation and development of the root system this mechanism is replaced by another. Analysis of photographs of the samples of substrates seeds obtained for the stage of root formation and growth (presented in Fig. 2) indicate the evident destruction of the polymer under the influence of germinated this roots. In this case, the roots of the plant create mechanical stresses in the polymer, which there are creation cracks, their fusion, leading to the formation of through holes. Indeed, the pictures (Fig. 2 a, b) which are demonstrate surface of seed carriers, obtained on the 9 the day, show the evident cracks and holes in the polymer (Fig. 2). It is important to note that in the samples of PHB are dominated by transverse holes, while in the PLA they are longitudinal, parallel to the surface of the film. The pattern of destruction of PHB and PLA corresponds to the nature of the root system. In the first polymer roots germinate in a perpendicular direction to the surface of the film, in the second – parallel to the surface. It can be assumed that the direction of growth and development of the root system in the nonwoven biopolymer material associated with the initiation of seed germination by enzymatic hydrolysis of the polymer carrier, developing on the surface or directed to the volume of the polymer. In turn, this may depend on the structure of the nonwoven material, the structure of their crystallites and amorphous regions, on the nature of the polymer, which determines the mechanism of its biodegradation [13, 27]. Besides the mechanisms of destruction of the polymer carrier of seeds by enzymatic hydrolysis and mechanical action, another mechanism of destruction is possible. Another process in which the biodegradable polymer carrier of seeds can destroy, affecting the stage
  • 21. Norwegian Journal of development of the International Science No 27/2019 21 of plant growth is the ability of the polymer to participate in radical reactions [28]. Mechanical destruction that occurs in the polymer under the action of roots may rouse the appearance of free radicals. In addition, the main direction of biochemical processes in the germinating seed, which is enzymatic hydrolysis of starch and lipids, which is in the mass of the seed, may be accompanied by the formation of an excess of free radicals that can destroy cell structures, therefore, lead to cell death. Contact of germinating seeds with macromolecules of the polymer substrate through an aqueous medium can lead to the interaction of free radicals, which may pick out from the seed into water, with the functional bonds of the macromolecules contacting with it. Resulting in the reaction of transfer of free valence (r*) from the cell molecule (MH) into the polymer macromolecule (RH), which is convert the kinetic chains of oxidation of cell molecules, protects them from destruction, i.e., the polymer carrier in relation to the cells acts as an antioxidant. At the same time, the oxidation process can be initiated in polymer macromolecules by the following reaction [28]: MH → r* RH+ r* —> R* + rH Thus, oxidation of the polymer carrier significantly accelerates the destruction of its amorphous regions. It can be thought that the ability of the polymer matrix to break off the kinetic chains of the oxidative process in cells promotes the development of anabolic reactions of cell growth and, therefore, can accelerate the growth of the root system and plant germs. It is explains the acceleration of the development of wheat sprouts at a more advanced stage of plant growth on the substrate PHB (Fig. 1). Ability to assess the contribution of enzymatic hydrolysis, mechanical degradation and radical process into summary process of biodegradation of polymer carriers during seed germination may by definite by comparing the energy parameters of melting crystal structures of polymers. That estimated calculation was made for nonwoven material PHB. Known high sensitivity of wheat seeds to the energy effects, causing the flow of biochemical processes, in particular enzymatic processes. Reducing the energy barrier causing the participation of enzymes can occur due to the decomposition of macromolecules or decomposition of crystal structures. In this work, the activation energy of crystallite melting Ea was estimated. For this purpose, the Kissinger equation (Kissinger) was used for thermograms obtained by heating the sample at a constant rate [29]. The equation is based on the dependence of the fixed temperature on the polymer heating rate: Еa = [RТ1Т2 /(Т2 -Т1)] ln(V2/V1), (3) where Еa – activation energy, R- Universal gas constant, Т1, Т2 – temperature in K, corresponding to heating rates of the sample V1 и V2. Ea was determined with the help of equation (3). It were establish the change in the maximum melting point (Tmax), its shift according at the speed of heating in the range of 4 to 16 degrees/min, defined with respect to the standard (In). The obtained values Ea. are presented in table. 6. As can be seen from this table, enzymatic hydrolysis of PHB leads to a significant drop in the activation energy of crystallite melting. The low value of Ea indicates a high degree of defectiveness of the structure of the crystallites as a consequence of their destruction. It is important to emphasize the fact that Ea of the crystallites of PHB treated with root enzymes are lower than those treated with amylase (table 6). The value of Ea in a sample of PHB with sprouted roots is also reduced compared to the original polymer, and is close to the sample treated with water, which may indicate the process of polymer destruction occurring under the action of sprouted seeds, as a process mainly occurring in amorphous areas. Conclusion Analysis of the dynamics of changes in the parameters of wheat growth on polymer substrates shows that the process of seed germination and growth of the root system of the plant is autocatalytic and correlates with the destruction of the polymer material. Based on the data obtained, it follows that the processes of destruction of polymeric materials stimulate seed germination and plant growth. In turn, the processes of seed germination are initiated degradation of polymers. Destruction of the polymeric carrier of wheat seeds from biodegradable material includes several mechanisms depending on the stage of plant development. Comparison of processes of destruction of materials from PHB and PLA, occurring in the absence of contact with the plant, shows the acceleration of the destruction of the polymer under the action of extract of amylase, isolated from the seeds and enzymes isolated from the root system of wheat. Comparison of the melting parameters of the samples of polymeric substrates after enzymatic hydrolysis with parameters of the samples obtained after germination of the root system lets make a guess that the effect of polymeric carrier on the rate of germination of wheat seeds is depend on process of enzymatic hydrolysis of the substrate at the stage of ontogenesis and radical processes of mechanodestruction and oxidation of the polymer at the stage of growth and development of plant. The nonwoven materials PHB and PLA are most suitable in quality carriers of seeds. Ability of these polymers to show the stimulating action to the plant seeds depends on structural parameters, which define the ability to swell and chemical stability in an aqueous solution of enzymes and activity to oxidative destruction. Due to the different location of amorphous and crystalline regions in the fibers of nonwoven PLA compared with PHB changes the direction of growth the root system.
  • 22. 22 Norwegian Journal of development of the International Science No 27/2019 Table 1. Indicators of germination and biometric parameters of wheat seed seedlings of the "Athena" variety (Triticum aestivum). Sample № Characteristics of the sample-substrate in a Petri dish **Seed germina- tion, % ** Massa, g *Energy germinations seeds', % **Length root, cm **Height plants, cmFull plant root 1 2 3 4 5 6 7 Control (filter paper) PLA extruded film PLA non-woven material PHB extruded film PHB non-woven material PHB+SCN pressed film PHB+SCN nonwoven material 86±2 88±2 92±2 90±2 96±2 96±2 96±2 0.156±0.008 0.114±0.008 0.184±0.01 0.124±0.008 0.178±0.01 0.160±0.01 0.196±0.01 0.035±0.002 0.020±0.001 0.054±0.003 0.028±0.002 0.050±0.003 0.048±0.002 0.050±0.003 80±2 50±5 70±2 55±5 96±1 94±1 94±1 7.8±1.0 5.6±1.5 12.0±2.0 8.2±1.8 10.4±1.5 9.4±2.0 9.8±1.0 117±2 118±5 125±5 120±5 135±5 125±5 138±5 Note: *the germination energy, defined on the 3 day. ** data obtained on the 7th day of seed germination Table 2. The dynamics of germination of wheat seeds on different carriers Characteristics of the sample material of the substrate seed The solvent from which the obtained nonwoven material The number of germinated seeds. Germination index, GIon the 1-st day on the 2-nd day on the 3-rd day on the 4-th day on the 7-th day Control PLA extruded film PLA non-woven material PHB extruded film PHB non-woven material PHB non-woven material PHB+SCN nonwoven fabric PHB+SCN nonwoven fabric - - CHF - CHF CHF + EDC CHF CHF + EDC 0 0 0 0 0 0 0-2 2-3 5-7 0 7-10 3-5 5-7 6-7 46-47 10-46 35-40 5-8 25-27 5-7 45-48 45-48 47-48 45-49 43-44 25-30 47-48 24-26 47-49 48-49 47-49 47-49 43-45 35-40 47-48 39-41 47-49 48-49 47-50 47-50 0.60-0.62 0.40-0.41 0.63-0.65 0.44-0.46 0.69-0.72 0.70-0.71 0.81-0.82 0.72-0.81 Table 3. The mass of samples of initial films and after germination of seeds in them Characteristics of the samples sample series № Sample mass, g PHB non-woven material initial PHB after seed germination PLA non-woven material source PLA after seed germination 1 2 1 2 1 2 1 2 0.0189±0.002 0.0182±0.002 0.0102±0.002 0.0098±0.001 0.0494±0.005 0.0445±0.005 0.022±0.003 0.0197±0.002 Table 4. Physical and mechanical characteristics of seed substrates of nonwoven PHB, PLA initial and after germination of wheat seeds in them Characteristics of the samples sample series № Relative elongation, % The maximum load, H Breaking length, m PHB nonwoven material initial PHB after seed germination PLA nonwoven initial material PLA after seed germination 1-2 1-2 1-2 1-2 2.4-3.9 1.0-1.1 30.2-86.1 6.6-16.3 0.9-1.4 0.5-0.9 1.3-1.6 3.7-4.0 406.3-454.7 201.0-364.7 175.1-194.3 1073.0-1129.0 Note: measurement Error of physical and mechanical parameters, ±20%
  • 23. Norwegian Journal of development of the International Science No 27/2019 23 Table 5. Thermophysical parameters of polymer samples of the substrates - carriers of the seed from nonwoven material* Characteristics of the sample material of the substrate seed Temperature, Т, о си Hm, J/g χ, % , day Тм 1 Tmax Тм 2 PHB (CHF) initial after seed germination PHB (CHF + EDC) initial after seed germination PHB+SCN (CHF) source after seed germination PHB+SCN (CHF + EDC) initial after seed germination PLA (CHF) initial after seed germination After seed germination 156.0 158.0 160.0 156.0 162.0 153.0 147.0 159.0 152.0 156.0 152.0 175.0 173.5 172.8 169.8 173.0 170.0 172.0 170.0 168.9 170.2+ shoulder 164.0 162.5+ shoulder 160.0 190.0 184.0 185.0 180.0 180.0 179.0 177.0 179.0 174.0 174.0 168.0 61.3 34.1 65.2 59.7 62.8 20.8 61.2 17.6 41.0 36.0 35.0 68.1 37.9 72.4 66.3 69.7 23.1 68.0 19.5 38.6 34.0 33.0 0 9 0 9 0 9 0 9 0 9 14 *Note: Tm1 - initial temperature of the melting peak, Tmax. Temperature at the maximum peak of melting, Tm2 - final melting peak temperature, Hm. - melting heat, χ is the degree of crystallinity, the time of seed germination. Table 6. The thermophysical parameters of samples of nonwoven material PHB, treated with water and extract with am- ylase and enzymes Characteristicss samples The temperature of the maximum melting peak Tmax, 0 C The heat of fusion H, J/g Crystallinity de- gree , % Activation energy of melting of crystallites of PHB Ea, kJ/mol PHB nonwoven initial mate- rial PHB after germination of seeds with the appearance of roots (more than 9 days) PHB nonwoven material after saturation with water PHB nonwoven material after saturation with amylase from an aqueous seed extract PHB nonwoven material after the saturation of the enzyme from the aqueous extract of the roots 172.0-174.0 170.0-174.0 170.0+ shoulder 164 164.0+ shoulder 160.0 160.0+ shoulder 157.0 62.9 33.2 60.0 57.1 51.0 69.9 36.9 66.7 63.4 56.7 500±20 470±30 450±60 209±30 169±20 REFERENCES: 1. Mikhailina V.I. The use of polymers in agriculture. Rus.: Primenenie polymerov v cel`ckom hozyastve. Moscow: WHITEISH, 1973.- 76 p. 2. Handbook of Plastic Films / Editor: E. M Abdel Bari. Shawbury, Shrewsbury, Shropshire: Rapra Technology Limited, 2003.- 352 p. 3. Spirin A. P., Izmailov Y. A., Sizov O. A., Izvekov A. S. “Minimum mulch tillage” // Rus: Technika v cel`skom chozyaistve (Technique in agriculture). 2008.- No. 1.- P. 27-32. 4. Zhirmunskaya N. M. “Environmentally friendly farming on the garden plot (with the basics of biodynamics)” M.: Marketing, 1996. - P. 93 - 97. 5. Patent of Russian Federation № 2019944. 1994. Zayavka No. 4802221/15 (publ. 30.09.1994). Zlotin B. L., Garayev A. I. “The Seed tape”. 6. Patent of Russian Federation № 2547716. 2015. Zayavka No. 2013151476/13 (publ.10.04.2015). Izmailov A. Yu., Elizarov V. P., Lobachevsky J. P. and others. “ Machine for sowing seed in the tape”. 7. Volova T.G., Vinogradova O.N., Zhila N.O. et al. “Physicochemical Properties of Multicomponent
  • 24. 24 Norwegian Journal of development of the International Science No 27/2019 Polyhydroxyalkanoates: Novel Aspects”// Polym. Sci. Ser.A. 2017. -V. 59. - N 1. - P.98-106. 8. Tertyshnaya Yu.V., Shibryaeva L.S. “Degradation of Poly(3-hydroxybutyrate) and Its Blends During Treatment With UV Light and Water” // Polym Sci. Ser. B. - 2013. -V. 55.- N 3-4. - P. 164 - 168. 9. Podzorova M.V., Popov A.A., Tertyshnaya Y.V “Environmentally friendly films based on poly(3- hydroxybutyrate) and poly(lactic acid): A Review”. // Russian Journal of Physical Chemistry B. - 2014. - V. 8. - N 5. - P. 726-732. 10. Shibryaeva L.S., Tertyshnaya Yu.V., Pal'mina D.D., Levina N.S. “The Biodegraded Polymers as Materials for Sowing of Grain Crops Seeds” // Rus.: Cel`skochozyastvennye mashiny (Agricultural machinery and technology). - 2015. - N 6. - P.14-18. 11. Tertyshnaya Yu.V., Shibryaeva L.S. "Biodegradable Polymers: Prospects of Their Large- Scale Application in Industry of Russia”// Rus.: Ecology and industry of Russia. - 2015. - N. 8. - P. 20- 25. 12. Araujo W.F., Botrel T.A. “Influence of CO2 applied with the irrigation water and plastic mulch on Summer Squash” // Rev. Cienc. agron. - 2010. - V. 41. - N 2. - Р. 216-221. 13. Tertyshnaya Y.V., Shibryaeva L.S., Ol`khov A.A. “Thermal Oxidation and Degradation of Poly-3- hydroxybutyrate Nonwoven Materials” // Russian Journal of Physical Chemistry. B. - 2015. - V.9. - N 3. - P.498-503. 14. Bonartsev A.P., Bonartseva G.A., Artsis M.I., Iordanskii A.L., Zaikov G.E. “Biodegradation and medical application of microbial poly(3- hydroxybutyrate)” // Molecular Crystals and Liquid Crystals. - 2012. - V. 555. - N 232-262. DOI:10.1080/15421406.2012.635549 15. Ol'khov A.A, Sklyanchuk E.D., Abbasov T.A. et al. “Regeneration Potential of a New Tendon Implant Made of Polyhydroxybutyrate Nanofibres” // Rus.: Technologii zhivyich sistem (Technology of living systems). - 2015. - V. 12. - N 2. - P. 3-11. 16. Shishatskaya E.I., Kamendov I.V., Starosvetsky S.I., et al. “An in vivo study of osteoplastic properties of resorbable poly-3- hydroxybutyrate in models of segmental osteotomy and chronic Osteomyelitis” // Artificial Cells, Nanomedicine, and Biotechnology. - 2014. - N 40. - P. 344-355. 17. GOST 12038-84. “Seeds of agricultural crops. Methods for determining seed germination”. Enter. 01.07.86. Moscow: Publishing house of standards, 1990. - 29 p. 18. Filatov Yu. N. “Electroforming of fibrous materials (EFF- process)” / Editor V. N. Kirichenko. Moscow: Oil and gas, 1997. - 298 p. 19. Matveev, A. T., Afanasov I. M. “Obtaining nanofibers method of electroforming” / Textbook for students. Moscow: MGU, 2010. - 83 p. 20. Ol`khov A.A., Vlasov C.V., Shibryaeva L.S. et al. “Structural Features of LDPE-Poly(3- hydroxybutyrate) Blends”// Polymer Science. Ser. A. - 2000. - V. 42. - N 4. - P.447-452. 21. Sarasua J.R., Lopez A.A., Balerdi P., Maiza I. “Crystallization and Thermal Behavior of Optically Pure Polylactides and Their Blends” // J. Mater. Sci. - 2005. - V. 40. - N 8. - P.1855-1862. 22. GOST 4650-80 (ST SEV 1692-79) Plastics. Methods for determination of water absorption of the ISS 83.080 AXTU 2209, date of introduction 1980-12- 01. 23. Metlitsky, L. V. Rus: Biochimiya na strazhe urozhaya (Biochemistry of the charge of the harvest). Moscou: Science, 1965. - 183 p. 24. Obroucheva N.V., Sinkevich I.A., Lityagina S.V., Novikova G.V. “ Water Relations in Germinating Seeds”// Russian Journal of Plant Physiology. - 2017. - V.64. - N 4. - P. 625-633. 25. Iordanskii A.L., Kamaev P.P. “The Effect of Water Immobilization on Its Sorption and Diffusion in Poly(3-oxybutyrate)” // Rus.: Visocomolekulyarniye soedineniya (High molecular weight compounds) Ser. А. - 1998. - V. 40. - N 1. - P.94-95. 26. Kamaev P.P., Aliev I.I., Iordanskii A.L., Wasserman A.M. “Molecular dynamics of the spin probes in dry and wet poly(3-hydroxybutyrate) films with different morphology // Polymer. - 2001. - V.42. - N 2. - P.515-520. 27. Hasirci V. Biodegradable Biomedical Polymers. Review of Degradation and in Vivo Responses to Polylactides and Polyhydroxyalkanoates. Biomaterials and Bioengineering Handbook / Editor: D. L. Wise. New York: Marcel Dekker, 2000. - P. 141. 28. Emanuel N.M., Buchachenko A.L Rus.:”Chemical physics of molecular destruction and stabilization of polymers”. Moscow: Nauka, 1988. - 368 p. 29. Chan J. H.,Balke S.T.//Polym. Degrad. Stability.-1997. - V. 57. - N 1. - P.135-149.
  • 25. Norwegian Journal of development of the International Science No 27/2019 25 MEDICAL SCIENCES УДК 616.993:078-08.084 EVALUATION OF DEGREE OF IMMUNE DYSFUNCTION AS OF CYTOKINES IN PATIENTS WITH LIVER ECHINOCOCCOSIS Bodnya K. Kharkiv Medical Academy of Postgraduate Education, Ministry of Health of Ukraine Velieva T. Kharkiv Medical Academy of Postgraduate Education, Ministry of Health of Ukraine Bodnya I. Kharkiv Medical Academy of Postgraduate Education, Ministry of Health of Ukraine ОЦІНКА СТУПЕНЯ ІМУННОЇ ДИСФУНКЦІЇ ЗА СТАНОМ ЦИТОКІНОВОЇ СИСТЕМИ У ХВОРИХ НА ЕХІНОКОКОЗ ПЕЧІНКИ Бодня К.І. Харківська медична академія післядипломної освіти МОЗ України Велієва Т.А. Харківська медична академія післядипломної освіти МОЗ України Бодня І.П. Харківська медична академія післядипломної освіти МОЗ України Abstract The paper presents the results of the study of the current situation in echinococcosis, he characteristic of the basic diagnostic methods is given and the treatment-diagnostic algorithm is optimized, which improves the results of treatment. 73 patients with echinococcosis and cytokines IL-1β, IL-1 Ra, IL-4, IL-8, IFN-γ were examined іn order to evaluate the state of the cytokine system. Анотація В роботі представлені результати вивчення сучасної ситуації з ехінококозу, дана характеристика основних методів діагностики та оптимізовано діагностичний алгоритм, що покращує результати лікування. З метою оцінки стану цитокінової системи у хворих на ехінококоз обстежено 73 особи та були досліджені цитокіни IL-1β, IL-1 Ra, IL-4, IL-8, IFN-γ. Keywords: echinococcosis, diagnostics, cytocine IL-1β, IL-1 Ra, IL-4, IL-8, IFN-γ. Ключові слова: ехінококоз, діагностика, цитокіни IL-1β, IL-1 Ra, IL-4, IL-8, IFN-γ. Ехінококоз печінки тяжке паразитарне захво- рювання, яке зустрічається у жителів всієї земної кулі, але має різну тенденцію до поширення в різ- них географічних регіонах. Однак необхідно відзна- чити, що офіційно наведені дані не завжди відобража- ють дійсну частоту захворюваності. Так, в Чилі, що є одним з осередків ехінококозу, в результаті проведе- ного узагальненого аналізу офіційних даних, публіка- цій в літературі і безпосередньої роботи в госпіталях встановлено, що ехінококоз зустрічається у 8,5-11,4 на кожні 100 тисяч населення, що в 4 рази перевищує офіційні дані [1]. Такая же ситуация наблюдается и в Украине: по официальным данным захворюваність на ехінококоз превышает данные официальной статис- тики. Серед країн СНД ендемічними регіонами є Ре- спубліки Середньої Азії, Молдова і деякі регіони Росії. Захворюваність на ехінококоз в Турк- меністані, Молдові, Киргизстані становить 3,8-5,5 на 100 тисяч населення [2, 3]. В Узбекистані рівень ураження на ехінококоз варіює в середньому від 6 до 9 осіб на 100 тисяч населення. Кількість щорічних операцій в цій республіці становить 1-1,5 тисяч з летальністю 2,5-7% і більше [3]. Незважаючи на доброякісну природу, ехінококоз є однією з про- блемних областей хірургічної гепатології, через часті ускладнення і тривалі терміни стаціонарного ліку- вання. Будучи крайовою патологією, ехінококоз довгі роки залишається однією з головних проблем цен- трально-азіатського регіону [4, 5]. Територія України є осередком напруженості епізоотичних процесів, до яких відноситься і ехіноко- коз, частота якого має стійку тенденцію до збільшення. Однокамерний ехінокок паразитує в личинковій стадії у проміжного хазяїна − більш ніж у 60 видів тра- воїдних і всеїдних копитних тварин, а у статевозрілій стадії − у 15 видів м'ясоїдних, включаючи вовка, ша- кала, які є остаточними хазяями [6, 7]. Існуючі труд- нощі ранньої і диференціальної діагностики, обумов- лені тривалим безсимптомним перебігом хвороби, пі- знім зверненням хворих за медичною допомогою, коли вже спостерігаються ускладнені форми ехіноко- козу печінки, а киста досягає великих розмірів, ство- рюють тактичні і технічні складнощі при проведенні оперативного втручання [8, 9, 10]. Найбільш частими є хронічні ускладнення: нагноєння паразитарної ки- сти, яке зустрічається у 18,4-49% випадків, звапніння фіброзної капсули – у 4,8-18,1% осіб [11, 12]. Частота гострих ускладнень ехінококозу, таких